EP0551390B1 - Amides de l'acide gras de polyhydroxy dans des compositions detergentes contenant un agent antisalissures - Google Patents

Amides de l'acide gras de polyhydroxy dans des compositions detergentes contenant un agent antisalissures Download PDF

Info

Publication number
EP0551390B1
EP0551390B1 EP91918418A EP91918418A EP0551390B1 EP 0551390 B1 EP0551390 B1 EP 0551390B1 EP 91918418 A EP91918418 A EP 91918418A EP 91918418 A EP91918418 A EP 91918418A EP 0551390 B1 EP0551390 B1 EP 0551390B1
Authority
EP
European Patent Office
Prior art keywords
soil release
alkyl
fatty acid
release agent
anionic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91918418A
Other languages
German (de)
English (en)
Other versions
EP0551390A1 (fr
Inventor
Robert Ya-Lin Pan
Eugene Paul Gosselink
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0551390A1 publication Critical patent/EP0551390A1/fr
Application granted granted Critical
Publication of EP0551390B1 publication Critical patent/EP0551390B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds

Definitions

  • This invention pertains to laundry detergent compositions containing soil release agent. More particularly, this invention pertains to laundry detergents having enhanced soil release agent performance through the use of certain polyhydroxy fatty acid amide surfactants.
  • soil release agents have been suggested for use in detergent compositions in order to enhance grease and oil cleaning of detergent compositions for synthetic fibers and fabrics.
  • Synthetic textiles such polyesters, polyacrylamides (e.g. nylon), and acrylics typically have hydrophobic surfaces which make removal of grease- and oil-type stains difficult.
  • Soil release agents are compounds having both hydrophobic and hydrophilic sections. The hydrophobic portion of the soil release agent adheres to the surfaces of the synthetic fibers or fabric, and the hydrophilic portion of the soil release agent increases hydrophilicity of the surface of the synthetic material. Once deposited, these soil release agents enhance cleaning ability of detergents in subsequent washings since grease and oil are more easily removed from the hydrophilized fabric surface.
  • anionic materials such as anionic detersive surfactants and builder salts, can interfere with soil release agent performance and, hence, impair overall cleaning ability of the detergent.
  • the formulator of liquid detergent compositions can face an especially difficult challenge because the type of soil release agent best suited for liquid detergents typically are characterized by having nonionic hydrophile sections (which typically comprise ethoxylate monomeric units) that have a strong propensity to interact with anionic surfactants.
  • Detergent compositions can be easily prepared which do not include surfactant systems that significantly interact with soil release agents by eliminating or severely reducing the level of anionic surfactant present in the formulation.
  • anionic surfactants is often highly desirable in detergent compositions for superior cleaning ability across a broad spectrum of stains.
  • Conventional nonionic surfactants can be added to the composition to assist in overall detergency performance, however it remains desirable to provide compositions containing anionic surfactants and soil release agents which have both enhanced soil release agent efficiency and improved overall detergent performance, especially improved grease/oil cleaning ability.
  • N-acyl, N-methyl glucamides for example, are disclosed by J. W. Goodby, M. A. Marcus, E. Chin, and P. L. Finn in "The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles," Liquid Crystals, 1988, Volume 3, No. 11, pp 1569-1581, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R. Hilgenfeld in "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem.
  • N-alkyl polyhydroxyamide surfactants have been of substantial interest recently for use in biochemistry, for example in the dissociation of biological membranes. See, for example, the journal article "N-D-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry," Biochem. J. (1982), Vol. 207, pp 363-366, by J. E. K. Hildreth.
  • N-alkyl glucamides in detergent compositions has also been discussed.
  • U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and G.B. Patent 809,060, published February 18, 1959, assigned to Thomas Hedley & Co., Ltd. relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent.
  • These compounds include an N-acyl radical of a higher straight chain fatty acid having 10-14 carbon atoms.
  • These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It is also generally indicated that additional constituents to impart desirable properties to the composition can also be included in the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.
  • U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz relates to aqueous detergent compositions containing the condensation reaction product of N-alkyl glucamine and an aliphatic ester of a fatty acid.
  • the product of this reaction is said to be useable in aqueous detergent compositions without further purification.
  • PCT International Application WO 83/04412, published December 22, 1983, by J. Hildreth relates to amphiphilic compounds containing polyhydroxyl aliphatic groups said to be useful for a variety of purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparing liposomes.
  • R'CON(R)CH2R'' and R''CON(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R'' is the residue of an aldose.
  • European Patent 0 285 768 published October 12, 1988, H. Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C18 (preferably C1-C6) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide.
  • the thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc.
  • anionic surfactants such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates
  • nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether,
  • Paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionic surfactant shampoo formulations are exemplified.
  • the N-polyhydroxy alkyl fatty acid amides are said to have superior skin tolerance attributes.
  • U.S. Patent 2,982,737 issued May 2, 1961, to Boettner, et al., relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an N-alkylglucamide nonionic surfactant which is selected from N-methyl,N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.
  • glucamide surfactants are disclosed, for example, in DT 2,226,872, published December 20, 1973, H. W. Eckert, et al., which relates to washing compositions comprising one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis, improved by the addition of an N-acylpolyhydroxyalkyl-amine of the formula R1C(O)N(R2)CH2(CHOH) n -CH2OH, wherein R1 is a C1-C3 alkyl, R2 is a C10-C22 alkyl, and n is 3 or 4.
  • the N-acylpolyhydroxyalkyl-amine is added as a soil suspending agent.
  • U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al. relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxylalkyl compound of the formula R1N(Z)C(O)R2 wherein R1 is a C10-C22 alkyl, R2 is a C7-C21 alkyl, R1 and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CHOH) m CH2OH where m is 3 or 4.
  • U.S. Patent 4,021,539 issued May 3, 1977, to H. Möller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxylalkyl-amines which include compounds of the formula R1N(R)CH(CHOH) m R2 wherein R1 is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R1 but both cannot be H, and R2 is CH2OH or COOH.
  • French Patent 1,360,018, April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabilized against polymerization with the addition of amides of the formula RC(O)N(R1)G wherein R is a carboxylic acid functionality having at least seven carbon atoms, R1 is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.
  • German Patent 1,261,861, February 29, 1968, A. Heins relates to glucamine derivatives useful as wetting and dispersing agents of the formula N(R)(R1)(R2) wherein R is a sugar residue of glucamine, R1 is a C10-C20 alkyl radical, and R2 is a C1-C5 acyl radical.
  • G.B. Patent 745,036, published February 15, 1956, assigned to Atlas Powder Company, relates to heterocyclic amides and carboxylic esters thereof that are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc.
  • the compounds are expressed by the formula N(R)(R1)C(O)R2 wherein R is the residue of an anhydrized hexane pentol or a carboxylic acid ester thereof, R1 is a monovalent hydrocarbon radical, and -C(O)R2 is the acyl radical of a carboxylic acid having from 2 to 25 carbon atoms.
  • U.S. Patent 3,312,627 discloses solid toilet bars that are substantially free of anionic detergents and alkaline builder materials, and which contain lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(O)NR1(R2) wherein RC(O) contains from about 10 to about 14 carbon atoms, and R1 and R2 each are H or C1-C6 alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxyl groups of from 2 to about 6.
  • a substantially similar disclosure is found in U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.
  • the present invention provides a detergent composition containing one or more anionic surfactants and one or more soil release agents characterized by the presence of an anionic surfactant-interactive nonionic hydrophile or an anionic surfactant-interactive hydrophobic moiety, or both, and a soil release agent-enhancing amount of a polyhydroxy fatty acid amide surfactant of the formula: wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, R2 is C5-C31 hydrocarbyl, and Z is a polyhydroxylhydrocarbyl having a linear hydrocarbyl with at least 3 hydroxyls, or an alkoxylated derivative thereof.
  • the polyhydroxy fatty acid amides hereof both enhance soil release agent deposition and can improve grease/oil cleaning ability of the compositions.
  • soil release agent-enhancing amount is meant that the formulator of the composition is to incorporate an amount of this release agent that will enhance deposition of the soil release agent upon the fabrics that are cleaned, or otherwise enhance grease/oil cleaning performance of the detergent composition in a subsequent cleaning operation.
  • the amount of soil release agent will vary with the anionic surfactant selected, the concentration of anionic surfactant, and the particular soil release agent chosen.
  • the compositions will comprise at least about 1%, by weight, preferably at least about 3%, more preferably from 3% to 30%, of the polyhydroxy fatty acid amide, and at least about 4%, by weight, of the anionic surfactant component.
  • the soil release agents hereof will typically be utilized at levels ranging from .01% to 10%, by weight of the detergent composition.
  • the polyhydroxy fatty acid amides can provide excellent cleaning, including grease/oil stain cleaning especially when combined with anionic surfactants such as, but not limited to, alkyl sulfates, alkyl ester sulfonates, alkyl ethoxy sulfates, etc.
  • compositions hereof will comprise at least about 1%, typically from 3% to 50%, preferably from 3% to 30%, of the polyhydroxy fatty acid amide surfactant described below.
  • the polyhydroxy fatty acid amide surfactant component of the present invention comprises compounds of the structural formula: wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CHOH) n -CH2OH, -CH(CH2OH)-(CHOH) n-1 -CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.
  • R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott.
  • N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl
  • the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate,
  • the amount of catalyst is preferably from 0.5 mole % to 50 mole %, more preferably from 2.0 mole % to 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis.
  • the reaction is preferably carried out at from 138°C to 170°C for typically from 20 to 90 minutes.
  • the reaction is also preferably carried out using from 1 to 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamide surfactant, and mixtures thereof.
  • this process is carried out as follows:
  • N-linear glucosyl fatty acid amide product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate.
  • a detailed experimental procedure is provided below in the Experimental.
  • polyhydroxy "fatty acid” amide materials used herein also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petrochemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.
  • the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide.
  • the level of these by-products will vary depending upon the particular reactants and process conditions.
  • the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide.
  • the preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product.
  • the detergent compositions hereof will generally contain at least about 4%, by weight, of anionic surfactants, typically from 4% to 50%, preferably from 5% to 30%.
  • anionic detersive surfactants known in the art can be utilized in the detergent compositions hereof. Sulfate and sulfonate anionic surfactants are particularly contemplated for use, although others can also be utilized.
  • One type of anionic surfactant which can be utilized encompasses alkyl ester sulfonates. These are desirable because they can be made with renewable, non-petroleum resources. Furthermore, surprisingly good cleaning ability can be obtained for this type of surfactant when combined with the polyhydroxy fatty acid amides. Preparation of the alkyl ester sulfonate surfactant component can be effected according to known methods disclosed in the technical literature.
  • linear esters of C8-C20 carboxylic acids can be sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula: wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, and R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble salt-forming cation.
  • Suitable salts would include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g.
  • R3 is C10-C16 alkyl
  • R4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R3 is C14-C16 alkyl.
  • Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein.
  • Alkyl sulfate surfactants include water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and
  • Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactant. These surfactants are water soluble salts or acids typically of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12 ⁇ C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium, and quaternary ammonium cations such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
  • Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
  • anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C9-C20 linear alkylbenzenesulphonates C8-C22 primary or secondary alkanesulphonates
  • C8-C24 olefinsulphonates C8-C24
  • alkyl glycerol sulfonates 1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpol
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • compositions hereof will contain at least about 4% anionic surfactant, typically from 5% to 30% anionic surfactant.
  • compositions of the present invention comprise a soil release agent component having one or more of either anionic surfactant-interactive hydrophobic or anionic surfactant-interactive nonionic hydrophilic moieties, or both.
  • Soil release agents are polymeric (as used herein, polymeric includes oligomeric) compounds characterized by having both hydrophilic components, whose purpose it is to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic components, whose purpose it is to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • polyhydroxy fatty acid amide in detergent compositions also containing anionic surfactants can enhance performance of many of the more commonly utilized types of polymeric soil release agents.
  • Anionic surfactants can interfere with the ability of certain soil release agents to deposit upon and adhere to hydrophobic surfaces.
  • Many of these polymeric soil release agents are characterized by having nonionic hydrophile segments or hydrophobe segments which are anionic surfactant-interactive. The benefits of this invention are especially pronounced for anionic surfactants having low or zero degrees of ethoxylation.
  • compositions hereof for which improved polymeric soil release agent performance can be obtained through the use of polyhydroxy fatty acid amide are those which contain an anionic surfactant system, an anionic surfactant-interactive soil release agent, and a soil release agent-enhancing amount of the polyhydroxy fatty acid amide wherein: (I) anionic surfactant-interaction between the soil release agent and the anionic surfactant component of the detergent composition can be shown by a comparison of the level of soil release agent (SRA) deposition on hydrophobic fibers (e.g., polyester) in aqueous solution between (A) a "Control" test run wherein deposition of the SRA of the detergent composition in aqueous solution, in the absence of other detergent ingredients, is measured, and (B) an "SRA/Anionic surfactant" test run wherein the same type and amount of the anionic surfactant system utilized in detergent composition is combined in aqueous solution with the SRA of the Control test run, whereby reduced deposition in (B) relative to (A) indicates ani
  • the tests hereof should be conducted at anionic surfactant concentrations in the aqueous that are above the critical micelle concentration of the anionic surfactant and preferably above about 100 ppm.
  • the polymeric soil release agent concentration should be at least 15 ppm.
  • a swatch of polyester fabric should be used for the hydrophobic fiber source. Identical swatches are immersed and agitated in 35°C aqueous solutions for the respective test runs for a period of 12 minutes, then removed, and analyzed.
  • Polymeric soil release agent deposition level is determined by radiotagging the soil release agent prior to treatment and subsequently conducting radiochemical analysis, according to techniques known in the art.
  • soil release agent deposition can alternately be determined in the above test runs (i.e., test runs A, B, and C) by determination of ultraviolet light (UV) absorbance of the test solutions, according to techniques well known in the art. Decreased UV absorbance in the test solution after removal of the hydrophobic fiber material corresponds to increased SRA deposition. UV analysis, as will be understood by those skilled in the art, should not be utilized for test solutions containing types and amounts of materials which cause excessive UV absorbance interference, such as high concentration of surfactants with aromatic groups (e.g., alkyl benzene sulfonates, etc.).
  • surfactants with aromatic groups e.g., alkyl benzene sulfonates, etc.
  • soil release agent-enhancing amount of polyhydroxy fatty acid amide is meant an amount of such surfactant that will enhance deposition of the soil release agent upon hydrophobic fibers, as described above, or an amount for which enhanced grease/oil cleaning performance can otherwise be obtained for fabrics washed in the detergent composition hereof in the next subsequent cleaning operation.
  • the amount of polyhydroxy fatty acid amide will vary with the anionic surfactant selected, the concentration of anionic surfactant, and the particular soil release agent chosen.
  • compositions will comprise from 0.01% to 10%, by weight, of the polymeric soil release agent, typically from 0.1% to 5%, preferably from 0.02% to 3.0%, and from 4% to 50%, more typically from 5% to 30% of anionic surfactant.
  • Such compositions should generally contain at least about 1%, preferably at least about 3%, by weight, of the polyhydroxy fatty acid amide, though it is not intended to necessarily be limited thereto.
  • the polymeric soil release agents for which performance Is enhanced by polyhydroxy fatty acid amide in the presence of anionic surfactant include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 2 to 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2) n OCH2CH2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.
  • Cellulosic derivatives that are functional as soil release agents are commercially available and include hydroxyethers of cellulose such as Methocel R (Dow).
  • Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose.
  • C1-C4 alkyl and C4 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose.
  • a variety of cellulose derivatives useful as soil release polymers are disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al..
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C1-C6 vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Such materials are known in the art and are described in European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
  • Suitable commercially available soil release agents of this kind include the SokalanTM type of material, e.g., SokalanTM HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from 25:75 to 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from 300 to 2000.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976. See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 which discloses similar copolymers.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and 6:1.
  • this polymer include the commercially available material Zelcon R 5126 (from Dupont) and Milease R T (from ICI). These polymers and methods of their preparation are more fully described in U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone, said soil release agent being derived from allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2 propylene diol, wherein after sulfonation, the terminal moieties of each oligomer have, on average, a total of from about 1 to about 4 sulfonate groups.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J. J. Scheibel and E. P. Gosselink, U.S. Serial No. 07/474,709, filed January 29, 1990.
  • Suitable polymeric soil release agents include the ethyl-or methyl-capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al., the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy groups derived from polyethylene glycol (PEG), the block polyester oligomeric compounds of U.S.
  • PEG polyethylene glycol
  • Patent 4,702,857 issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X-(OCH2CH2) n - wherein n is from 12 to 43 and X is a C1-C4 alkyl, or preferably methyl.
  • Additional soil release polymers that can be used herein include certain of the soil release polymers of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
  • the terephthalate esters contain unsymmetrically substituted oxy-1,2-alkyleneoxy units.
  • Included among the soil release polymers of U.S. Patent 4,877,896 are materials with polyoxyethylene hydrophile components or C3 oxyalkylene terephthalate (propylene terephthalate) repeat units within the scope of the hydrophobe components of (b)(i) above. It is the soil release polymers characterized by either, or both, of these criteria that particularly benefit from the inclusion of the polyhydroxy fatty acid amides hereof, in the presence of anionic surfactants.
  • compositions hereof can optionally contain nonionic surfactants (in addition to the polyhydroxy fatty acid amide), other types of surfactants, as well as other detergent adjuncts.
  • additional surfactants will comprise generally from 0% to 30%, usually less than about 25%, of the detergent composition.
  • suitable auxiliary surfactants and other nonlimiting detergent adjuncts are described below.
  • Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.
  • Cationic detersive surfactants can also be included in detergent compositions of the present invention.
  • Cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula: [R2(OR3) y ] [R4(OR3) y ]2R5N+X ⁇ wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, ring structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6-CHOHCH2OH wherein R6 is any hex
  • Ampholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for examples of ampholytic surfactants.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants.
  • Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the detergents hereof can include one or more other detergent adjunct materials or other materials for assisting in or enhancing cleaning performance, treatment of the substrate to be cleaned or modifying the appearance, color, or other aesthetics of the compositions.
  • these include, but are not limited to, builders, enzymes, bleaching compounds, chelating agents, clay soil removal/anti-redeposition agents, polymeric dispersants, suds suppressors, brighteners, etc.
  • Detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hardness control.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • Liquid formulations typically comprise at least about 1%, more typically from 5% to 50%, preferably 5% to 30%, by weight of detergent builder.
  • Granular formulations typically comprise at least about 1%, more typically from 10% to 80%, preferably from 15% to 50% by weight of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions hereinafter, collectively “borate builders"
  • non-borate builders are used in the compositions of the invention intended for use at wash conditions less than about 50°C, especially less than about 40°C.
  • silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, Issued May 12, 1987 to H. P. Rieck.
  • layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839, Issued May 12, 1987 to H. P. Rieck.
  • other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are especially useful in the present invention.
  • Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula: M z (zAlO2 ⁇ ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate.
  • Preferred aluminosilicates are zeolite builders which have the formula: Na z [(AlO2) z (SiO2) y ] ⁇ xH2O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from about 15 to 264.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na12[(AlO2)12(SiO2)12] ⁇ xH2O wherein x is from 20 to 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.
  • phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-1, 1-diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzylmethylidene and halo methylidene phosphonates.
  • Phosphonate builder salts of the aforementioned types are disclosed in U.S. Patent Nos.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt.
  • alkali metals such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substituted ammonium (e.g., alkanolammonium) salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates.
  • a number of ether polycarboxylates have been disclosed for use as detergent builders.
  • Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972.
  • a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula: CH(A) (COOX)-CH(COOX)-O-CH(COOX)-CH(COOX) (B) wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
  • TDS tartrate disuccinic acid
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates represented by the structure: HO-[C(R) (COOM) -C(R) (COOM)-O] n -H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from 2 to 15 (preferably n is from 2 to 10, more preferably n averages from 2 to 4) and each R is the same or different and selected from hydrogen, C1 ⁇ 4 alkyl or C1 ⁇ 4 substituted alkyl (preferably R is hydrogen).
  • Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
  • Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
  • polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid and nitrilotriacetic acid.
  • polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citric builders e.g., citric acid and soluble salts thereof, is a polycarboxylate builder of particular importance for heavy duty liquid detergent formulations, but can also be used in granular compositions.
  • Suitable salts include the metal salts such as sodium, lithium, and potassium salts, as well as ammonium and substituted ammonium salts.
  • carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973.
  • succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • Alkyl succinic acids typically are of the general formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
  • succinate builders include laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dispersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polyacetal carboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
  • Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • organic builders known in the art can also be used.
  • monocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps.” Chain lengths of C10-C20 are typically utilized.
  • the hydrocarbyls can be saturated or unsaturated.
  • Detersive enzymes can be Included In the detergent formulations for a variety of reasons including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
  • the enzymes to be incorporated include proteases, lipases, amylases, cellulases and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name Esperase®. The preparation of this enzyme and analogous enzymes is described in British patent specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASETM and SAVINASETM by Novo Industries A/S (Denmark) and MAXATASETM by International Bio-Synthetics, Inc. (The Netherlands).
  • Protease A and Protease B are enzymes referred to herein as Protease A and Protease B.
  • Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985.
  • Protease B is a proteolytic enzyme which differs from Protease A in that it has a leucine substituted for tyrosine in position 217 in its amino acid sequence.
  • Protease B is described in European Patent Application Serial No. 87303761.8, filed April 28, 1987. Methods for preparation of Protease B are also disclosed in European Patent Application 130,756, Bott et al., published January 9, 1985.
  • Amylases include, for example, ⁇ -amylases obtained from a special strain of B.licheniforms, described in more detail in British patent specification No. 1,296,839 (Novo).
  • Amylolytic proteins include, for example, RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTM, Novo Industries.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, incorporated herein by reference, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent No. 1,372,034.
  • Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application No. 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
  • Lipase P Lipase P
  • Amano-P Lipase P
  • Such lipases of the present invention should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
  • Ouchterlony Acta. Med. Scan., 133, pages 76-79 (1950)
  • These lipases, and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent 4,707,291, Thom et al., issued November 17, 1987.
  • Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Psuedomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum , e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli .
  • Amano-P lipase the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/09813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically 0.05 mg to 3 mg, of active enzyme per gram of the composition.
  • the enzymes are preferably coated or prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques for accomplishing this are well known in the art.
  • an enzyme stabilization system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art.
  • one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate, and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, perferably formates. See, for example, U.S. Patent 4,318,818, Letton, et al., issued March 9, 1982.
  • the detergent compositions hereof may contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleach activators.
  • bleaching compounds When present bleaching compounds will typically be present at levels of from 1% to 20%, more typically from 1% to 10%, of the detergent composition.
  • bleaching compounds are optional components in non-liquid formulations, e.g., granular detergents. If present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • the compositions hereof not contain borate or material which can form borate in situ (i.e. borate-forming material) under detergent storage or wash conditions.
  • borate-forming material i.e. borate-forming material
  • detergents to be used at these temperatures are substantially free of borate and borate-forming material.
  • substantially free of borate and borate-forming material shall mean that the composition contains not more than about 2% by weight of borate-containing and borate-forming material of any type, preferably, no more than 1%, more preferably 0%.
  • One category of bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al., filed June 3, 1985, European Patent Application 0,133,354, Banks et al., published February 20, 1985, and U.S. Patent 4,412,934, Chung et al., issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns, et al..
  • bleaching agents that can be used encompasses the halogen bleaching agents.
  • hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • Preferred bleach activators incorporated into compositions of the present invention have the general formula: wherein R is an alkyl group containing from 1 to 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pK a in the range of from 4 to 13.
  • R is an alkyl group containing from 1 to 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pK a in the range of from 4 to 13.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al..
  • detergent compositions will contain 0.025% to 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions, typically 0.01% to 5%. These compounds are selected preferably from the group consisting of:
  • CMC carboxy methyl cellulose
  • Polymeric dispersing agents can advantageously be utilized in the compositions hereof. These materials can aid in calcium and magnesium hardness control. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.
  • Polycarboxylate materials which can be employed as the polymeric dispersing agent herein are these polymers or copolymers which contain at least about 60% by weight of segments with the general formula wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; a salt-forming cation and n is from 30 to 400.
  • X is hydrogen or hydroxy
  • Y is hydrogen or carboxy
  • Z is hydrogen
  • M is hydrogen, alkali metal, ammonia or substituted ammonium.
  • Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most prefereably from 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:1, more preferably from 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal/anti-redeposition agent.
  • Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
  • the detergent compositions herein may also optionally contain one or more iron and manganese chelating agents as a builder adjunct material.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally -substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, preferably 1.
  • these amino carboxylates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Operable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions.
  • Compounds with one or more, preferably at least two, units of the substructure wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates).
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Alkylene groups can be shared by substructures.
  • Polyfunctionally - substituted aromatic chelating agents are also useful in the compositions herein. These materials can comprise compounds having the general formula wherein at least one R is -SO3H or -COOH or soluble salts thereof and mixtures thereof.
  • U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. discloses polyfunctionally - substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes and 1,2-dihydroxy -3,5-disulfobenzene.
  • Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono-or triethanol-amine) salts.
  • these chelating agents will generally comprise from 0.1% to 10% by weight of the detergent compositions herein. More preferably chelating agents will comprise from 0.1% to 3.0% by weight of such compositions.
  • the choice of brightener for use in detergent compositions will depend upon a number of factors, such as the type of detergent, the nature of other components present in the detergent composition, the temperatures of wash water, the degree of agitation, and the ratio of the material washed to tub size.
  • the brightener selection is also dependent upon the type of material to be cleaned, e.g., cottons, synthetics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners which will be effective for a variety of fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible.
  • optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • Stilbene derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives of bis(triazinyl)amino-stilbene; bisacylamino derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.
  • Certain derivatives of bis(triazinyl)aminostilbene which may be useful in the present invention may be prepared from 4,4'-diaminestilbene-2,2'-disulfonic acid.
  • Coumarin derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-position, and in the 3- and 7-positions.
  • Carboxylic acid derivatives which may be useful in the present invention include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p -phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives.
  • Cinnamic acid derivatives which may be useful in the present invention can be further subclassified into groups which include, but are not necessarily limited to, cinnamic acid derivatives, styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference.
  • the styrylazoles can be further subclassified into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles, as disclosed on page 78 of the Zahradnik reference. It will be understood that these three identified subclasses may not necessarily reflect an exhaustive list of subgroups into which styrylazoles may be sub classified.
  • optical brighteners which may be useful in the present invention are the derivatives of dibenzothiophene-5,5-dioxide disclosed at page 741-749 of The Kirk-Othmer Encyclopedia of Chemical Technology , Volume 3, pages 737-750 (John Wiley & Son, Inc., 1962) and include 3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5 dioxide.
  • Another class of brighteners which may be useful in the present invention are the derivatives of 6-membered-ring hetero- cycles disclosed in the Kirk-Othmer reference. Examples of such compounds include brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide.
  • miscellaneous agents may also be useful as brighteners.
  • miscellaneous agents are disclosed at pages 93-95 of the Zahradnik reference, and include 1-hydroxy-3,6,8-pyrenetri- sulphonic acid; 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-di- phenylimidazolonedisulphonic acid; and derivatives of pyrazoline- quinoline.
  • optical brighteners which may be useful in the present invention are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PhorwhiteTM series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(styryl)bis-phenyls; and the y-aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis-(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis-(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole.
  • suds suppressors can be desirable because the polyhydroxy fatty acid amide surfactants hereof can increase suds stability of the detergent compositions. Suds suppression can be of particular importance when the detergent compositions include a relatively high sudsing surfactant in combination with the polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading automatic washing machines. These machines are typically characterized by having drums, for containing the laundry and wash water, which have a horizontal axis and rotary action about the axis. This type of agitation can result in high suds formation and, consequently, in reduced cleaning performance. The use of suds suppressors can also be of particular importance under hot water washing conditions and under high surfactant concentration conditions.
  • suds suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. These materials are a preferred category of suds suppressor for detergent compositions.
  • the detergent compositions may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example, list: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexaalkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., Na, K, Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 5°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo, et al..
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S..
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • compositions hereof will generally comprise from 0% to 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts thereof When utilized as suds suppressors, monocarboxylic fatty acids, and salts thereof, will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from .01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from .01% to 5.0%, although higher levels can be used.
  • compositions hereof A wide variety of other ingredients useful in detergent compositions can be included in the compositions hereof, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • the detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5.
  • Liquid product formulations preferably have a pH between 7.5 and 9.5, more preferably between 7.5 and 9.0. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • pH is preferably below about 9.0.
  • one suitable apparatus for use herein comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium.
  • the other two necks of the flask are fitted with a nitrogen sweep and a wide-bore side-arm (caution: a wide-bore side-arm is important in case of very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet.
  • the latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap.
  • a 500 watt heating mantle with a variable transformer temperature controller (“Variac”) used to heat the reaction is so placed on a lab-jack that it may be readily raised or lowered to further control temperature of the reaction.
  • Variac variable transformer temperature controller
  • N-methylglucamine (195 g., 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE 1270, 220.9 g., 1.0 mole) are placed in a flask.
  • the solid/liquid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes).
  • catalyst anhydrous powdered sodium carbonate, 10.5 g., 0.1 mole, J. T. Baker
  • the nitrogen sweep is shut off and the aspirator and nitrogen bleed are adjusted to give 0.17 bar (5 inches (5/31 atm.) Hg.) vacuum. From this point on, the reaction temperature is held at 150° C by adjusting the Variac and/or by raising or lowering the mantle.
  • compositions of Examples 1-4 represent condensed granular formulations prepared by slurrying and spray drying the base granule ingredients to a moisture of about 5%, and mixing in the additional dry ingredients in a compacting mixer. The resulting high density powder is dedusted by spraying on the liquid ingredients.
  • Examples 1-3 are intended for use at about 1050 ppm concentration, at wash temperatures less than about 50°C.
  • Example 4 is preferably utilized at a concentration of about 6000 ppm, at temperatures from 30°C to 95°C.
  • Examples 4-8 are prepared by combining non-aqueous solvents, aqueous surfactant pastes or solutions, melted fatty acids, aqueous solutions of polycarboxylate builders and other salts, aqueous ethoxylated tetraethylenpentamine, buffering agents, caustic, and the remaining water.
  • the pH is adjusted using either an aqueous citric acid solution or sodium hydroxide solution to about pH 8.5.
  • the final ingredients such as soil release agents, enzymes, colorants, and perfume, are added and the mixture stirred until a single phase is achieved.
  • Examples 5-7 are preferably utilized at about 2000 ppm, wash water weight basis, at temperatures below about 50°C.
  • Example 8 is preferably utilized at about 12,000 ppm, for wash temperatures from 30°C to 95°C.
  • An alternate method for preparing the polyhydroxy fatty acid amides used herein is as follows.
  • a reaction mixture consisting of 84.87g. fatty acid methyl ester (source: Procter & Gamble methyl ester CE1270), 75g. N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04g. sodium methoxide (source: Aldrich Chemical Company 16,499-2), and 68.51g. methyl alcohol is used.
  • the reaction vessel comprises a standard reflux set-up fitted with a drying tube, condenser and stir bar. In this procedure, the N-methyl glucamine is combined with methanol with stirring under argon and heating is begun with good mixing (stir bar; reflux).
  • the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution is completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point.
  • the reaction mixture is maintained at reflux for 4 hours. After removal of the methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, an overall yield of 106.92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regular sampling throughout the course of the reaction makes an overall percentage yield value meaningless.
  • the reaction can be carried out at 80% and 90% reactant concentrations for periods up to 6 hours to yield products with extremely small by-product formation.
  • polyhydroxy fatty acid amides are, by virtue of their amide bond, subject to some instability under highly basic or highly acidic conditions. While some decomposition can be tolerated, it is preferred that these materials not be subjected to pH's above about 11, preferably 10, nor below about 3 for unduly extended periods. Final product pH (liquids) is typically 7.0-9.0.
  • the detergent formulator will recognize that it is a simple and convenient matter to use an acid which provides an anion that is otherwise useful and desirable in the finished detergent composition.
  • citric acid can be used for purposes of neutralization and the resulting citrate ion ( ca . 1%) be allowed to remain with a ca . 40% polyhydroxy fatty acid amide slurry and be pumped into the later manufacturing stages of the overall detergent-manufacturing process.
  • the acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.
  • the polyhydroxy fatty acid amides derived from coconut alkyl fatty acids are more soluble than their tallow alkyl (predominantly C16-C18) counterparts. Accordingly, the C12-C14 materials are somewhat easier to formulate in liquid compositions, and are more soluble in cool-water laundering baths. However, the C16-C18 materials are also quite useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C16-C18 materials may be better detersive surfactants than their C12-C14 counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs . performance when selecting a particular polyhydroxy fatty acid amide for use in a given formulation.
  • solubility of the polyhydroxy fatty acid amides can be increased by having points of unsaturation and/or chain branching in the fatty acid moiety.
  • materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts.
  • polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc. will ordinarily be greater than the solubility of their monosaccharide-derived counterpart materials. This higher solubility can be of particular assistance when formulating liquid compositions.
  • polyhydroxy fatty acid amides wherein the polyhydroxy group is derived from maltose appear to function especially well as detergents when used in combination with conventional alkylbenzene sulfonate ("LAS") surfactants.
  • LAS alkylbenzene sulfonate
  • the polyhydroxy fatty acid amides can be manufactured not only from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose” corn syrup, "high maltose” corn syrup, etc. can conveniently and economically be used. De-lignified, hydrolyzed cellulose pulp can also provide a raw material source for the polyhydroxy fatty acid amides.
  • polyhydroxy fatty acid amides derived from the higher saccharides such as maltose, lactose, etc.
  • the more soluble polyhydroxy fatty acid amides can help solubilize their less soluble counterparts, to varying degrees.
  • the formulator may elect to use a raw material comprising a high glucose corn syrup, for example, but to select a syrup which contains a modicum of maltose (e.g., 1% or more).
  • the resulting mixture of polyhydroxy fatty acids will, in general, exhibit more preferred solubility properties over a broader range of temperatures and concentrations than would a "pure" glucose-derived polyhydroxy fatty acid amide.
  • the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages with respect to performance and/or ease-of-formulation.
  • some loss of grease removal performance may be noted at fatty acid maltamide levels above about 25% and some loss in sudsing above about 33% (said percentages being the percentage of maltamide-derived polyhydroxy fatty acid amide vs . glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary somewhat, depending on the chain length of the fatty acid moiety.
  • the formulator electing to use such mixtures may find it advantageous to select polyhydroxy fatty acid amide mixtures which contain ratios of monosaccharides (e.g., glucose) to di- and higher saccharides (e.g., maltose) from 4:1 to 99:1.
  • monosaccharides e.g., glucose
  • di- and higher saccharides e.g., maltose
  • the formulator of, for example, solid, typically granular, detergent compositions may find it convenient to run the process at 30°C-90°C in solvents which comprise ethoxylated alcohols, such as the ethoxylated (EO 3-8) C12-C14 alcohols, such as those available as NEODOL 23 EO6.5 (Shell).
  • ethoxylated alcohols such as the ethoxylated (EO 3-8) C12-C14 alcohols, such as those available as NEODOL 23 EO6.5 (Shell).
  • the industrial scale reaction sequence for preparing the preferred acyclic polyhydroxy fatty acid amides will comprise: Step 1 - preparing the N-alkyl polyhydroxy amine derivative from the desired sugar or sugar mixture by formation of an adduct of the N-alkyl amine and the sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by Step 2 - reacting the aforesaid polyhydroxy amine with, preferably, a fatty ester to form an amide bond.
  • Step 2 of the reaction sequence can be prepared by various art-disclosed processes, the following process is convenient and makes use of economical sugar syrup as the raw material. It is to be understood that, for best results when using such syrup raw materials, the manufacturer should select syrups that are quite light in color or, preferably, nearly colorless ("water-white").
  • Adduct Formation The following is a standard process in which about 420 g of about 55% glucose solution (corn syrup - about 231 g glucose - about 1.28 moles) having a Gardner Color of less than 1 is reacted with 119 g of about 50% aqueous methylamine (59.5 g of methylamine - 1.92 moles) solution.
  • the methylamine (MMA) solution is purged and shielded with N2 and cooled to about 10°C, or less.
  • the corn syrup is purged and shielded with N2 at a temperature of 10°-20°C.
  • the corn syrup is added slowly to the MMA solution at the indicated reaction temperature as shown.
  • the Gardner Color is measured at the indicated approximate times in minutes.
  • the time to reach substantial equilibrium concentration of the adduct is shortened by the use of higher ratios of amine to sugar.
  • equilibrium is reached in about two hours at a reaction temperature of about 30°C.
  • the time is at least about three hours.
  • the combination of amine:sugar ratio; reaction temperature; and reaction time is selected to achieve substantially equilibrium conversion, e.g., more than about 90%, preferably more than about 95%, even more preferably more than about 99%, based upon the sugar, and a color that is less than about 7, preferably less than about 4, more preferably less than about 1, for the adduct.
  • substantially equilibrium conversion e.g., more than about 90%, preferably more than about 95%, even more preferably more than about 99%, based upon the sugar, and a color that is less than about 7, preferably less than about 4, more preferably less than about 1, for the adduct.
  • the product after removal of water and MMA by evaporation, is about 95% N-methyl glucamine, a white powder.
  • the above procedure is repeated with about 23.1 g of Raney Ni catalyst with the following changes.
  • the catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with 13.8 bar gauge (200 psig) H2 and the reactor is pressurized with H2 at 110.4 bar gauge (1600 psig) for two hours, the pressure is released at one hour and the reactor is repressurized to 110.4 bar gauge (1600 psig).
  • the adduct is then pumped into the reactor which is at 13.8 bar gauge (200 psig) and 20°C, and the reactor is purged with 13.8 bar gauge (200 psig) H2, etc., as above.
  • the resulting product in each case is greater than about 95% N-methyl glucamine; has less than about 10 ppm Ni based upon the glucamine; and has a solution color of less than about Gardner 2.
  • the crude N-methyl glucamine is color stable to about 140°C for a short exposure time. It is important to have good adduct that has low sugar content (less than about 5%, preferably less than about 1%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about 1).
  • adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged and shielded with N2 at 10-20°C. About 330 g of about 70% corn syrup (near water-white) is degassed with N2 at about 50°C and is added slowly to the methylamine solution at a temperature of less than about 20°C. The solution is mixed for about 30 minutes to give about 95% adduct that is a very light yellow solution.
  • About 190 g of adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H2 at about 20°C.
  • the H2 pressure is raised to about 13.8 bar (200 psi) and the temperature is raised to about 50°C.
  • the pressure is raised to 17.2 bar (250 psi) and the temperature is held at 50-55°C for about three hours.
  • the product, which is about 95% hydrogenated at this point, is then raised to a temperature of about 85°C for about 30 minutes and the product, after removal of water and evaporation, is about 95% N-methyl glucamine, a white powder.
  • Ni content in the glucamine is about 100 ppm as compared to the less than 10 ppm in the previous reaction.
  • a 200 ml autoclave reactor is used following typical procedures similar to those set forth above to make adduct and to run the hydrogen reaction at various temperatures.
  • Adduct for use in making glucamine is prepared by combining about 420 g of about 55% glucose (corn syrup) solution (231 g glucose; 1.28 moles) (the solution is made using 99DE corn syrup from CarGill, the solution having a color less than Gardner 1) and about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air Products).
  • the adduct is used for the hydrogen reaction right after making, or is stored at low temperature to prevent further degradation.
  • the glucamine adduct hydrogen reactions are as follows:
  • the preparation of the tallow (hardened) fatty acid amide of N-methyl maltamine for use in detergent compositions according to this invention is as follows.
  • Step 1 of the foregoing reaction sequence can be conducted using commercial corn syrup comprising glucose or mixtures of glucose and, typically, 5%, or higher, maltose.
  • the resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions herein.
  • Step 2 of the foregoing reaction sequence can be carried out in 1,2-propylene glycol or NEODOL.
  • the propylene glycol or NEODOL need not be removed from the reaction product prior to its use to formulate detergent compositions.
  • the methoxide catalyst can be neutralized by citric acid to provide sodium citrate, which can remain in the polyhydroxy fatty acid amide.
  • the compositions herein can contain more or less of various suds control agents.
  • various suds control agents For dishwashing high sudsing is desirable so no suds control agent will be used.
  • a wide variety of suds control agents are known in the art and can be routinely selected for use herein. Indeed, the selection of suds control agent, or mixtures of suds control agents, for any specific detergent composition will depend not only on the presence and amount of polyhydroxy fatty acid amide used therein, but also on the other surfactants present in the formulation.
  • silicone-based suds control agents of various types are more efficient (i.e., lower levels can be used) than various other types of suds control agents.
  • the silicone suds control agents available as X2-3419 and Q2-3302 (Dow Corning) are particularly useful herein.
  • the formulator of fabric laundering compositions which can advantageously contain soil release agent has a wide variety of known materials to choose from (see, for example, U.S. Patents 3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and 4,877,896).
  • Additional soil release materials useful herein include the nonionic oligomeric esterification product of a reaction mixture comprising a source of C1-C4 alkoxy-terminated polyethoxy units (e.g., CH3[OCH2CH2]16OH), a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of poly(oxyethylene)oxy units (e.g., polyethylene glycol 1500); a source of oxyiso-propyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy units (e.g., ethylene glycol) especially wherein the mole ratio of oxyethyleneoxy units:oxyiso-propyleneoxy units is at least about 0.5:1.
  • a source of C1-C4 alkoxy-terminated polyethoxy units e.g., CH3[OCH2CH2]16OH
  • a source of terephthaloyl units e.g., di
  • Such nonionic soil release agents are of the general formula wherein R1 is lower (e.g., C1-C4) alkyl, especially methyl; x and y are each integers from 6 to 100; m is an integer of from 0.75 to 30; n is an integer from 0.25 to 20; and R2 is a mixture of both H and CH3 to provide a mole ratio of oxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
  • soil release agent useful herein is of the general anionic type described in U.S. Patent 4,877,896, but with the condition that such agents be substantially free of monomers of the HOROH type wherein R is propylene or higher alkyl.
  • the soil release agents of U.S. Patent 4,877,896 can comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid
  • these additional soil release agents can comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid.
  • Such agents are preferred for use in granular laundry detergents.
  • the formulator may also determine that it is advantageous to include a non-perborate bleach, especially in heavy-duty granular laundry detergents.
  • a non-perborate bleach especially in heavy-duty granular laundry detergents.
  • peroxygen bleaches are available, commercially, and can be used herein, but, of these, percarbonate is convenient and economical.
  • the compositions herein can contain a solid percarbonate bleach, normally in the form of the sodium salt, incorporated at a level of from 3% to 20% by weight, more preferably from 5% to 18% by weight and most preferably from 8% to 15% by weight of the composition.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3. 3H2O2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
  • a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate
  • the percarbonate can be incorporated into detergent compositions without additional protection, but preferred embodiments of the invention utilize a stable form of the material (FMC).
  • sodium silicate of SiO2:Na2O ratio from 1.6:1 to 2.8:1, preferably 2.0:1, applied as an aqueous solution and dried to give a level of from 2% to 10% (normally from 3% to 5%), of silicate solids by weight of the percarbonate.
  • Magnesium silicate can also be used and a chelant such as one of those mentioned above can also be included in the coating.
  • the particle size range of the crystalline percarbonate is from 350 micrometers to 450 micrometers with a mean of approximately 400 micrometers. When coated, the crystals have a size in the range from 400 to 600 micrometers.
  • the percarbonate While heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction mixture, the percarbonate still requires protection from heavy metals present as impurities in other ingredients of the product. It has been found that the total level of iron, copper and manganese ions in the product should not exceed 25 ppm and preferably should be less than 20 ppm in order to avoid an unacceptably adverse effect on percarbonate stability.
  • the following relates to the preparation of a preferred liquid heavy duty laundry detergent according to this invention.
  • the stability of enzymes in such compositions is considerably less than in granular detergents.
  • typical enzyme stabilizers such as formate and boric acid
  • lipase and cellulase enzymes can be protected from degradation by protease enzymes.
  • lipase stability is still relatively poor in the presence of alkylbenzene sulfonate (“LAS”) surfactants.
  • LAS alkylbenzene sulfonate
  • LAS alkylbenzene sulfonate
  • liquid detergent compositions containing lipase, protease and cellulase enzymes can be particularly troublesome in liquid compositions. It is particularly challenging to provide such tertiary enzyme systems in stable liquid detergents together with an effective blend of detersive surfactants. Additionally, it is difficult to incorporate peroxidase and/or amylase enzymes stably in such compositions.
  • liquid detergent compositions typically contain LAS or mixtures of LAS with surfactants of the RO(A) m SO3M type ("AES") noted hereinabove, i.e., LAS/AES mixtures.
  • the liquid detergents herein preferably comprise binary mixtures of the AES and polyhydroxy fatty acid amides of the type disclosed herein. While minimal amounts of LAS can be present, it will be appreciated that the stability of the enzymes will be lessened thereby. Accordingly, it is preferred that the liquid compositions be substantially free (i.e., contain less than about 10%, preferably less than about 5%, more preferably less than about 1%, most preferably 0%) of LAS.
  • the water-soluble anionic surfactant herein preferably comprises (“AES"): RO(A) m SO3 M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl (C10-C24) group, A is an ethoxy or propoxy unit, m is an integer greater than 0 and M is hydrogen or a cation.
  • R is an unsubstituted C12-C18 alkyl group, A is an ethoxy unit, m is from 0.5 to 6, and M is a cation.
  • the cation is preferably a metal cation (e.g., sodium-preferred, potassium, lithium, calcium, magnesium, etc.) or an ammonium or substituted ammonium cation.
  • the ratio of the above surfactant ("AES”) to the polyhydroxy fatty acid amide herein be from 1:2 to 8:1, preferably 1:1 to 5:1, most preferably 1:1 to 4:1.
  • liquid compositions herein may alternatively comprise polyhydroxy fatty acid amide, AES, and from 0.5% to 5% of the condensation product of C8-C22 (preferably C10-C20) linear alcohol with between 1 and 25, preferably between 2 and 18, moles of ethylene oxide per mole of alcohol.
  • the liquid compositions herein preferably have a pH in a 10% solution in water at 20°C of from 6.5 to 11.0, preferably from 7.0 to 8.5.
  • compositions preferably further comprise from 0.1% to 50% of detergency builder.
  • These compositions preferably comprise from 0.1% to 20% of citric acid, or water-soluble salt thereof, and from 0.1% to 20% of a water-soluble succinate tartrate, especially the sodium salt thereof, and mixtures thereof, or from 0.1% to 20% by weight of oxydisuccinate or mixtures thereof with the aforesaid builders.
  • 0.1%-50% alkenyl succinate can also be used.
  • the preferred liquid compositions herein comprise from 0.0001% to 2%, preferably 0.0001% to 1%, most preferably 0.001% to 0.5%, on an active basis, of detersive enzyme.
  • detersive enzymes are preferably selected from the group consisting of protease (preferred), lipase (preferred), amylase, cellulase, peroxidase, and mixtures thereof.
  • Preferred are compositions with two or more classes of enzymes, most preferably where one is a protease.
  • lipases of interest include Amano AKG and Bacillis Sp lipase (e.g., Solvay enzymes). Also, see the lipases described in EP A 0 399 681, published November 28, 1990, EP A 0 218 272, published April 15, 1987 and PCT/DK 88/00177, published May 18, 1989.
  • Suitable fungal lipases include those producible by Humicola lanuginosa and Thermomyces lanuginosus . Most preferred is the lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae , as described in European Patent Application 0 258 068 commercially available under the trade name LIPOLASE.
  • lipase units of lipase per gram (LU/g) of product can be used in these compositions.
  • a lipase unit is that amount of lipase which produces 1 ⁇ mol of titratable butyric acid per minute in a pH stat, where pH is 7.0, temperature is 30°C, and substrate is an emulsion tributyrin and gum arabic, in the presence of Ca++ and NaCl in phosphate buffer.
  • Example 1 illustrates a preferred heavy duty liquid detergent composition
  • a preferred heavy duty liquid detergent composition comprising:
  • 2Protease B is a modified bacterial serine protease described in European Patent Application Serial No. 87 303761 filed April 28, 1987, particularly pages 17, 24 and 98.
  • 3Lipase used herein is the lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae , as described in European Patent Application 0 258 068, commercially available under the trade name LIPOLASE (ex Novo Nordisk A/S, Copenhagen Denmark).
  • 4Cellulase used herein is sold under the trademark CAREZYME (Novo Nordisk, A/S, Copenhagen Denmark).
  • 5Brightener 36 is commercially available as TINOPAL TAS 36.
  • the brightener is added to the composition as a separately prepared pre-mix of brightener (4%), monoethanolamine (60%) and water (35.5%).
  • a liquid laundry detergent composition suitable for use at the relatively high concentrations common to front-loading automatic washing machines, especially in Europe, and over a wide range of temperatures is as follows.
  • the fatty acid glucamide surfactant can be replaced by an equivalent amount of the maltamide surfactant, or mixtures of glucamide/maltamide surfactants derived from plant sugar sources.
  • the use of ethanolamides appears to help cold temperature stability of the finished formulations.
  • the use of sulfobetaine (aka “sultaine”) surfactants provides superior sudsing.
  • the formulator of high sudsing compositions will desirably avoid the introduction of suds-suppressing amounts of such fatty acids into high sudsing compositions with the polyhydroxy fatty acid amides, and/or avoid the formation of C14 and higher fatty acids on storage of the finished compositions.
  • One simple means is to use C12 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine surfactants can overcome some of the negative sudsing effects caused by the fatty acids.
  • anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% and greater) of anionic or polyanionic substituents such as the polycarboxylate builders may find it useful to pre-mix the brightener with water and the polyhydroxy fatty acid amide, and then to add the pre-mix to the final composition.
  • Polyglutamic acid or polyaspartic acid dispersants can be usefully employed with zeolite-built detergents.
  • AE fluid or flake and DC-544 are other examples of useful suds control agents herein.
  • compositions containing nonionic or anionic preferably sulfophthaloyl, sulfo-isophthaloyl or sulfobenzoyl type
  • nonionic or anionic preferably sulfophthaloyl, sulfo-isophthaloyl or sulfobenzoyl type

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Abstract

Est décrite une composition détergente contenant un ou plusieurs tensioactifs anioniques et un ou plusieurs agents antisalissures, caractérisée par la présence d'une fraction hydrophile non ionique interactive avec le tensioactif anionique, et/ou d'une fraction hydrophobe interactive avec le tensioactif anionique, ou des deux, et d'une quantité, activant l'agent antisalissures, d'un tensioactif d'amides de l'acide gras de polyhydroxy de formule (I) dans laquelle R1 est H, hydrocarbyl C¿1?-C4, 2-hydroxy éthyle, 2-hydroxy propyle, ou un mélange de ceux-ci, R2 est hydrocarbyle C5-C31, et Z est un polyhydroxyhydrocarbyle possédant une chaîne hydrocarbyle linéaire avec au moins trois hydroxyles directement reliés à la chaîne, ou bien son dérivé alcoxylé.

Claims (13)

  1. Composition détergente offrant un avantage de libération des salissures, comprenant un ou plusieurs tensioactifs anioniques ou non ioniques et un ou plusieurs agents anioniques ou non ioniques de libération des salissures, lesdits agents de libération des salissures comportant des constituants hydrophiles et des constituants hydrophobes, et comprenant soit (a) un ou plusieurs constituants hydrophiles non ioniques essentiellement constitués: (i) de segments polyoxyéthylène ayant un degré de polymérisation d'au moins 2; ou (ii) de segments oxypropylène ou polyoxypropylène ayant un degré de polymérisation de 2 à 10, où lesdits segments hydrophiles n'englobent pas les oxypropylènes non liés à des groupements adjacents à chaque extrémité par des liaisons éther, ou (iii) d'un mélange de motifs oxyalkylène comprenant des motifs oxyéthylène et de 1 à 30 motifs oxypropylène, comprenant au moins 25% de motifs oxyéthylène; soit (b) un ou plusieurs constituants hydrophobes comprenant: (i) des segments oxyalkylène(C₃)téréphtalate dans lesquels, si lesdits constituants hydrophobes comprennent aussi des motifs oxyéthylènetéréphtalate, le rapport des motifs oxyéthylènetéréphtalate aux motifs oxyalkylène(C₃)téréphtalate est de 2:1 ou inférieur; (ii) des segments alkylène en C₄-C₆ ou oxyalkylène en C₄-C₆, ou un mélange de ceux-ci; (iii) des segments poly(ester vinylique) ayant un degré de polymérisation d'au moins 2; ou (iv) des substituants éther alkylique en C₁-C₄ ou éther hydroxyalkylique en C₄, ou un mélange de ceux-ci, dans lesquels lesdits substituants sont présents sous forme de dérivés alkyl(en C₁-C₄)-éthercelluloses ou hydroxyalkyl(en C₄)éthercelluloses, ou d'un mélange de ceux-ci, et lesdits dérivés de cellulose sont amphiphiles, ou une combinaison de (a) et de (b), ladite composition étant caractérisée en ce qu'elle comprend une quantité améliorant la libération des salissures d'un tensioactif polyhydroxylamide d'acide gras de formule:
    Figure imgb0024
     dans laquelle R¹ est H, un groupe hydrocarbyle en C₁-C₄, 2-hydroxyéthyle, 2-hydroxypropyle, ou un mélange de ceux-ci, R² est un groupe hydrocarbyle en C₅-C₃₁, et Z est un groupe polyhydroxyhydrocarbyle possédant une chaîne hydrocarbyle linéaire ayant au moins 3 groupes hydroxyle liés directement à ladite chaîne, ou des dérivés alcoxylés de ceux-ci, et à condition que l'agent de libération des salissures ne soit pas la carboxyméthylcellulose.
  2. Composition selon la revendication 1, dans laquelle l'agent de libération des salissures est un ester anionique oligomère ou polymère.
  3. Composition selon la revendication 2, dans laquelle l'agent de libération des salissures est un ester anionique et contient des groupes sulfophtaloyle, sulfoisophtaloyle ou sulfobenzoyle.
  4. Composition selon la revendication 3, dans laquelle l'agent de libération des salissures comprend des constituants hydrophiles comprenant du polyoxyéthylène, et des segments hydrophobes essentiellement constitués de motifs éthylène- ou propylènetéréphtalate, ou de mélanges de ceux-ci.
  5. Composition selon la revendication 1, dans laquelle l'agent de libération des salissures comprend des segments poly(acétate de vinyle) greffés sur du polyoxyéthylène.
  6. Composition selon la revendication 1, dans laquelle ledit agent de libération des salissures comprend des éthers amphiphiles de cellulose avec des substituants alkyle en C₁-C₄ ou hydroxybutyle, ou leurs mélanges.
  7. Composition selon la revendication 1, dans laquelle R¹ est un groupe méthyle, R² est un groupe alkyle ou alcényle en C₉-C₁₇, et Z est dérivé d'un sucre réducteur.
  8. Composition selon la revendication 1, dans laquelle, pour ce qui est de ce polyhydroxylamide d'acide gras, Z est dérivé du glucose, du maltose ou du fructose.
  9. Composition selon la revendication 1, qui comprend aussi au moins 4% d'un tensioactif sulfate ou sulfonate anionique choisi dans le groupe constitué par les alkylsulfates, les alkylbenzènesulfonates, les alkylsulfates éthoxylés, les paraffinesulfonates et les alkylestersulfonates, et leurs mélanges.
  10. Composition détergente selon la revendication 9, comprenant au moins 4%, en poids, dudit tensioactif anionique, au moins 1%, en poids, dudit polyhydroxylamide d'acide gras, et de 0,1% à 5,0%, en poids, dudit agent de libération des salissures.
  11. Procédé pour améliorer la performance d'agents de libération des salissures dans des solutions de lavage aqueuses en présence de compositions détergentes contenant des tensioactifs anioniques et des agents anioniques ou non ioniques de libération des salissures qui ne sont pas de la carboxyméthylcellulose, ledit procédé étant caractérisé en ce qu'il comprend l'incorporation dans ladite composition détergente ou dans ladite solution de lavage aqueuse d'une quantité améliorant la libération des salissures de polyhydroxylamide d'acide gras de formule:
    Figure imgb0025
     dans laquelle R¹ est H, un groupe hydrocarbyle en C₁-C₄, 2-hydroxyéthyle, 2-hydroxypropyle, ou un mélange de ceux-ci, R² est un groupe hydrocarbyle en C₅-C₃₁, et Z est un groupe polyhydroxyhydrocarbyle possédant une chaîne hydrocarbyle linéaire ayant au moins 3 groupes hydroxyle liés directement à ladite chaîne, de préférence un N-méthylglucamide en C₁₁-C₁₇, un N-méthylmaltamide en C₁₁-C₁₇, ou des mélanges de ce glucamide et de ce maltamide, ou un dérivé alcoxylé de ceux-ci.
  12. Procédé selon la revendication 11, dans lequel ledit groupement R² dans ledit polyhydroxylamide d'acide gras, est un groupe alkyle ou alcényle en C₁₅-C₁₇, ou un mélange de ceux-ci.
  13. Procédé selon la revendication 11, dans lequel l'agent de libération des salissures est un, ester anionique oligomère ou polymère, comprenant de préférence des groupes sulfophtaloyle, sulfoisophtaloyle ou sulfobenzoyle.
EP91918418A 1990-09-28 1991-09-25 Amides de l'acide gras de polyhydroxy dans des compositions detergentes contenant un agent antisalissures Expired - Lifetime EP0551390B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US590637 1984-03-19
US59063790A 1990-09-28 1990-09-28
US75609291A 1991-09-06 1991-09-06
US756092 1991-09-06
PCT/US1991/007021 WO1992006152A1 (fr) 1990-09-28 1991-09-25 Amides de l'acide gras de polyhydroxy dans des compositions detergentes contenant un agent antisalissures

Publications (2)

Publication Number Publication Date
EP0551390A1 EP0551390A1 (fr) 1993-07-21
EP0551390B1 true EP0551390B1 (fr) 1995-11-15

Family

ID=27080901

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91918418A Expired - Lifetime EP0551390B1 (fr) 1990-09-28 1991-09-25 Amides de l'acide gras de polyhydroxy dans des compositions detergentes contenant un agent antisalissures

Country Status (17)

Country Link
US (1) US5332528A (fr)
EP (1) EP0551390B1 (fr)
JP (1) JPH06501734A (fr)
CN (1) CN1035827C (fr)
AU (1) AU8854991A (fr)
BR (1) BR9106912A (fr)
CA (1) CA2092186C (fr)
DE (1) DE69114716T2 (fr)
ES (1) ES2079680T3 (fr)
HU (1) HUT64784A (fr)
IE (1) IE913411A1 (fr)
MX (1) MX9101368A (fr)
NZ (1) NZ240028A (fr)
SK (1) SK25293A3 (fr)
TR (1) TR26007A (fr)
TW (1) TW223113B (fr)
WO (1) WO1992006152A1 (fr)

Families Citing this family (305)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5750485A (en) * 1991-06-18 1998-05-12 The Procter & Gamble Company Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol
US5241340A (en) * 1991-08-14 1993-08-31 Coulter Corporation Electrophotographic microfilm camera/processor apparatus
SE502396C2 (sv) * 1991-09-30 1995-10-16 Berol Nobel Ab Alkaliskt rengöringsmedel innehållande alkylglykosid samt medel för dess framställning
US5298195A (en) * 1992-03-09 1994-03-29 Amway Corporation Liquid dishwashing detergent
US5576277A (en) * 1992-03-10 1996-11-19 The Procter & Gamble Company Granular detergent compositions
EP0631608B1 (fr) * 1992-03-16 1996-07-17 The Procter & Gamble Company Compositions fluides renfermant des amides d'acides gras polyhydroxy
EP0572723A1 (fr) * 1992-06-02 1993-12-08 The Procter & Gamble Company Compositions détergentes liquides structurées
US5691294A (en) * 1993-03-30 1997-11-25 The Procter & Gamble Company Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica
DE4323253C1 (de) * 1993-07-12 1995-01-05 Henkel Kgaa Verwendung von Fettsäure-N-alkylpolyhydroxyalkylamiden als Klarspülmittel für die maschinelle Reinigung harter Oberflächen
US5534182A (en) * 1993-07-12 1996-07-09 Rohm And Haas Company Process and laundry formulations for preventing the transfer of dye in laundry processes
US5397506A (en) * 1993-08-20 1995-03-14 Ecolab Inc. Solid cleaner
US5866525A (en) * 1993-09-07 1999-02-02 Colgate-Palmolive Company Laundry detergent compositions containing lipase and soil release polymer
US5489393A (en) * 1993-09-09 1996-02-06 The Procter & Gamble Company High sudsing detergent with n-alkoxy polyhydroxy fatty acid amide and secondary carboxylate surfactants
US5500150A (en) * 1993-09-09 1996-03-19 The Procter & Gamble Company Solidified detergent additive with n-alkoxy polyhydroxy fatty acid amide and alkoxylated surfactant
US5510049A (en) * 1993-09-09 1996-04-23 The Procter & Gamble Company Bar composition with N-alkoxy or N-aryloxy polyhydroxy fatty acid amide surfactant
DE4331297A1 (de) * 1993-09-15 1995-03-16 Henkel Kgaa Stückseifen
DE4337032C1 (de) * 1993-10-29 1995-05-24 Henkel Kgaa Verwendung von Detergensgemischen zur Herstellung von Toilettensteinen
EP0659870A1 (fr) * 1993-11-26 1995-06-28 The Procter & Gamble Company Des compositions de N-Alcoyl amide d'acide gras polyhydroxy et procédé de synthése
CA2177681C (fr) * 1993-12-14 1999-10-19 Rajan Keshav Panandiker Detergents liquides a lessive contenant de l'acide polyamine et du polyalkyleneglycol
DE4400632C1 (de) * 1994-01-12 1995-03-23 Henkel Kgaa Tensidgemische und diese enthaltende Mittel
ES2132631T5 (es) * 1994-01-25 2011-02-17 THE PROCTER & GAMBLE COMPANY Composiciones detergentes líquidas o gelificadas para lavar vajillas de acción poco severa y alta jabonadura que contienen óxidos de aminas de cadena larga.
GB2288185A (en) * 1994-01-25 1995-10-11 Procter & Gamble Detergent compositions
DE4409321A1 (de) * 1994-03-18 1995-09-21 Henkel Kgaa Detergensgemische
US5866524A (en) * 1994-03-30 1999-02-02 Procter & Gamble Company Foamed cleaning compositions and method of treating textile fabrics
US5783546A (en) * 1994-04-22 1998-07-21 Procter & Gamble Company Amylase-containing detergent compositions
USH1513H (en) * 1994-06-01 1996-01-02 The Procter & Gamble Company Oleoyl sarcosinate with polyhydroxy fatty acid amides in cleaning products
USH1635H (en) * 1994-06-01 1997-03-04 The Procter & Gamble Company Detergent compositions with oleoyl sarcosinate and amine oxide
CA2191563A1 (fr) * 1994-06-01 1995-12-07 Serge Gabriel Pierre Roger Cauwberghs Composition detergente liquide contenant des tensioactifs de types sarcosinates d'oleoyle et anioniques
USH1514H (en) * 1994-06-01 1996-01-02 The Procter & Gamble Company Detergent compositions with oleoyl sarcosinate and polymeric dispersing agent
US5759982A (en) * 1994-06-17 1998-06-02 The Procter & Gamble Company Laundry bars with polyethylene glycol as a processing aid
US5500153A (en) * 1994-07-05 1996-03-19 The Procter & Gamble Company Handwash laundry detergent composition having improved mildness and cleaning performance
GB2292155A (en) * 1994-08-11 1996-02-14 Procter & Gamble Handwash laundry detergent composition comprising three surfactants
US5955416A (en) * 1994-08-23 1999-09-21 The Procter & Gamble Company Detergent compositions comprising lipolytic enzymes
EP0698659A1 (fr) * 1994-08-23 1996-02-28 The Procter & Gamble Company Compositions détergentes contenant des enzymes lipolytiques
EP0709451A1 (fr) * 1994-10-28 1996-05-01 The Procter & Gamble Company Compositions détergentes liquides stabiles
US5712243A (en) * 1994-12-02 1998-01-27 Lever Berothers Company, Division Of Conopco, Inc. Intimate admixtures of salts of 2,2'-oxydisuccinate (ODS) with selected glycolipid based surfactants to improve the flow and handling characteristics of the (ODS) salt
US5714455A (en) * 1994-12-02 1998-02-03 Lever Brothers Company, Division Of Conopco, Inc. Intimate admixtures of salts of sulfo carboxymethyloxy succinate (SCOMS) with selected glycolipid based surfactants to improve the flow and handling
US5616282A (en) * 1995-05-11 1997-04-01 Lever Brothers Company, Division Of Conopco, Inc. Amido peroxycarboxylic acid enhanced bleaching through combination with a fatty amide substituted sugar
US5942479A (en) * 1995-05-27 1999-08-24 The Proctor & Gamble Company Aqueous personal cleansing composition with a dispersed oil phase comprising two specifically defined oil components
GB9510833D0 (en) 1995-05-27 1995-07-19 Procter & Gamble Cleansing compositions
GB9510838D0 (en) * 1995-05-27 1995-07-19 Procter & Gamble Cleansing compositions
GB9510839D0 (en) * 1995-05-27 1995-07-19 Procter & Gamble Cleansing Compositions
JPH11505840A (ja) * 1995-05-27 1999-05-25 ザ、プロクター、エンド、ギャンブル、カンパニー クレンジング組成物
US5985809A (en) * 1995-05-27 1999-11-16 The Procter & Gamble Company Aqueous personal cleansing compositions comprising specific nonocclusive liquid polyol fatty acid polyester
US6777003B1 (en) 1995-06-07 2004-08-17 Cognis Corporation Iodine complex of alkyl polyglycosides
DE19533539A1 (de) 1995-09-11 1997-03-13 Henkel Kgaa O/W-Emulgatoren
US6420329B1 (en) * 1995-10-26 2002-07-16 S. C. Johnson & Son, Inc. Cleaning compositions
WO1997016517A1 (fr) * 1995-10-30 1997-05-09 The Procter & Gamble Company Compositions detergentes liquides epaissies, tres aqueuses, economiques
DE19544710C2 (de) 1995-11-30 1998-11-26 Henkel Kgaa Verdickungsmittel
US5932535A (en) * 1995-12-21 1999-08-03 Henkel Kommanditgesellschaft Auf Aktien Process for the production of light-colored, low-viscosity surfactant concentrates
DE19548068C1 (de) 1995-12-21 1997-06-19 Henkel Kgaa Verfahren zur Herstellung hellfarbiger, niedrigviskoser Tensidkonzentrate
FR2744132B1 (fr) * 1996-01-31 1998-04-24 Rhone Poulenc Chimie Systeme de base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin, sous forme d'une dispersion ou de granules et son utilisation en detergence
US5888949A (en) * 1996-03-08 1999-03-30 Henkel Corporation Composition for cleaning textile dyeing machines
US5756446A (en) * 1996-05-07 1998-05-26 Henkel Corporation Sugar surfactants having enhanced tactile properties
US6046147A (en) * 1996-08-13 2000-04-04 Henkel Corporation Process for making skin cleansing combination soap bars and cleansing liquids
US5922663A (en) 1996-10-04 1999-07-13 Rhodia Inc. Enhancement of soil release with gemini surfactants
AR010265A1 (es) * 1996-11-01 2000-06-07 Procter & Gamble Composiciones detergentes para el lavado a mano que comprende una combinacion de surfactantes y polimero de liberacion de suciedad
DK0958342T3 (da) 1996-12-31 2003-10-27 Procter & Gamble Fortykkede stærkt vandige væskeformige detergentsammensætninger
EP0958341A1 (fr) 1996-12-31 1999-11-24 The Procter & Gamble Company Compositions detersives liquides epaissies, fortement aqueuses, bon marche, contenant des tensioactifs aromatiques
US5962398A (en) * 1997-01-14 1999-10-05 Lever Brothers Company Isotropic liquids incorporating anionic polymers which are not hydrophobically modified
US6159921A (en) * 1997-02-28 2000-12-12 Henkel Corporation Dye transfer inhibition system
US5919312A (en) * 1997-03-18 1999-07-06 The Procter & Gamble Company Compositions and methods for removing oily or greasy soils
US6060441A (en) * 1997-04-10 2000-05-09 Henkel Corporation Cleaning compositions having enhanced enzyme activity
US5846923A (en) * 1997-07-08 1998-12-08 Rhodia Inc. Polyamphoteric phosphate ester surfactants
US5994286A (en) * 1997-07-22 1999-11-30 Henkel Corporation Antibacterial composition containing triclosan and tocopherol
DE19735715A1 (de) 1997-08-18 1999-02-25 Huels Chemische Werke Ag Amphiphile Polymere auf Basis von Polyestern mit einkondensierten acetalischen Gruppen, die bei Raumtemperatur flüssig sind, sowie ihr Einsatz in Wasch- und Reinigungsmitteln
US6099589A (en) * 1997-12-30 2000-08-08 Kay Chemical Company Presoak detergent with optical brightener
BRPI0415764A (pt) * 2003-11-28 2006-12-26 Eastman Chem Co interpolìmero, produto de reação, métodos para converter uma hidroxila, para preparar uma forma estável de um interpolìmero, para converter um álcool primário, e para tratar um mamìfero necessitado do mesmo, composições para revestimento e farmacêutica oral, dispersão de pigmento, e, artigo
GB0415905D0 (en) * 2004-07-16 2004-08-18 Reckitt Benckiser Nv Enzymes as active oxygen generators in cleaning compositions
US20060052269A1 (en) 2004-09-01 2006-03-09 Panandiker Rajan K Premoistened disposable wipe
KR100641006B1 (ko) 2004-11-04 2006-11-02 엘지.필립스 엘시디 주식회사 인쇄판
EP1851298B1 (fr) 2005-02-17 2010-03-24 The Procter and Gamble Company Composition de soin de tissus
DE102005025933B3 (de) 2005-06-06 2006-07-13 Centrotherm Photovoltaics Gmbh + Co. Kg Dotiergermisch für die Dotierung von Halbleitern
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US7666963B2 (en) * 2005-07-21 2010-02-23 Akzo Nobel N.V. Hybrid copolymers
PL1754781T3 (pl) 2005-08-19 2013-09-30 Procter & Gamble Stała kompozycja detergentowa do prania zawierająca anionowy środek powierzchniowo czynny i technologię wspomagania wapniem
JP2009511700A (ja) 2005-10-24 2009-03-19 ザ プロクター アンド ギャンブル カンパニー 有機シリコーンマイクロエマルションを含む布地手入れ組成物および系、並びにその使用方法
US7678752B2 (en) * 2005-10-24 2010-03-16 The Procter & Gamble Company Fabric care composition comprising organosilicone microemulsion and anionic/nitrogen-containing surfactant system
CN101370925B (zh) * 2006-01-23 2014-03-26 美利肯公司 含噻唑鎓染料的洗熨护理组合物
JP5378995B2 (ja) * 2006-06-12 2013-12-25 ローディア インコーポレイティド 親水化された基材及び基材の疎水性表面を親水化するための方法
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US20080020961A1 (en) * 2006-07-21 2008-01-24 Rodrigues Klin A Low Molecular Weight Graft Copolymers
US20080177089A1 (en) 2007-01-19 2008-07-24 Eugene Steven Sadlowski Novel whitening agents for cellulosic substrates
CA2675259A1 (fr) * 2007-02-09 2008-08-21 The Procter & Gamble Company Systemes de parfums
US7487720B2 (en) 2007-03-05 2009-02-10 Celanese Acetate Llc Method of making a bale of cellulose acetate tow
CA2690602C (fr) * 2007-06-12 2017-02-28 Rhodia Inc. Composition de nettoyage pour surface dure avec agent d'hydrophilisation et procede pour nettoyer des surfaces dures
CA2690744A1 (fr) * 2007-06-12 2008-12-24 Rhodia, Inc. Esters de mono-, di- et polyol alkoxylate phosphate utilises dans des formulations d'hygiene buccodentaire et procedes d'utilisation
CA2690607A1 (fr) * 2007-06-12 2008-12-18 Rhodia Inc. Composition de lessive avec agent antisalissure d'hydrophilisation et procedes d'utilisation de celle-ci
JP5613558B2 (ja) 2007-06-12 2014-10-22 ローディア インコーポレイティド パーソナルケア配合物中の、モノ−、ジ−及びポリオールホスフェートエステル
US20080318832A1 (en) * 2007-06-19 2008-12-25 Robb Richard Gardner Liquid detergent compositions with low polydispersity polyacrylic acid based polymers
RU2434041C1 (ru) * 2007-07-20 2011-11-20 Родиа Инк. Способ извлечения сырой нефти из подземной формации
DE102007038029A1 (de) * 2007-08-10 2009-02-12 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit polyesterbasiertem Soil-Release-Polymer
EP2071017A1 (fr) * 2007-12-04 2009-06-17 The Procter and Gamble Company Composition de détergent
ES2568784T5 (es) * 2008-01-04 2023-09-13 Procter & Gamble Una composición detergente para lavado de ropa que comprende glicosil hidrolasa
EP2083065A1 (fr) * 2008-01-22 2009-07-29 The Procter and Gamble Company Compositions de soin de couleur
EP2103676A1 (fr) 2008-03-18 2009-09-23 The Procter and Gamble Company Composition détergente pour le lavage du linge comprenant un sel de magnésium d'acide diamine-n'n' disuccinique d'éthylène
EP2103675A1 (fr) 2008-03-18 2009-09-23 The Procter and Gamble Company Composition détergente comprenant un polymère cellulosique
EP2103678A1 (fr) 2008-03-18 2009-09-23 The Procter and Gamble Company Composition détergente comprenant un co-polyester d'acides dicarboxyliques et de diols
US7923426B2 (en) * 2008-06-04 2011-04-12 The Procter & Gamble Company Detergent composition
EP2135931B1 (fr) 2008-06-16 2012-12-05 The Procter & Gamble Company Utilisation d'un polymère de libération de salissures dans des compositions de traitement des tissus
EP2135933B1 (fr) * 2008-06-20 2013-04-03 The Procter and Gamble Company Composition de lavage
ES2430858T3 (es) 2008-06-20 2013-11-22 The Procter & Gamble Company Composición para lavado de ropa
EP2154235A1 (fr) 2008-07-28 2010-02-17 The Procter and Gamble Company Procédé pour préparer une composition détergente
EP2163608A1 (fr) 2008-09-12 2010-03-17 The Procter & Gamble Company Particule pour composition de lavage comprenant un colorant azurant et du savon
EP2166077A1 (fr) 2008-09-12 2010-03-24 The Procter and Gamble Company Particules contenant un azurant optique
EP2166078B1 (fr) 2008-09-12 2018-11-21 The Procter & Gamble Company Particule pour composition de lavage comprenant un colorant azurant
US8232431B2 (en) * 2008-09-22 2012-07-31 The Procter & Gamble Company Specific branched surfactants and consumer products
US7994369B2 (en) 2008-09-22 2011-08-09 The Procter & Gamble Company Specific polybranched polyaldehydes, polyalcohols, and surfactants, and consumer products based thereon
EP2210520A1 (fr) 2009-01-22 2010-07-28 The Procter & Gamble Company Paquet comprenant un matériau adhésif de fourniture de parfum
US20100305019A1 (en) * 2009-06-01 2010-12-02 Lapinig Daniel Victoria Hand Fabric Laundering System
EP2451932A1 (fr) 2009-07-09 2012-05-16 The Procter & Gamble Company Procédé de lessive d'un tissu utilisant une composition détergente de lessive compactée
US20110009307A1 (en) 2009-07-09 2011-01-13 Alan Thomas Brooker Laundry Detergent Composition Comprising Low Level of Sulphate
WO2011005913A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Composition catalytique de détergent pour lessive comprenant des taux relativement bas d'électrolyte soluble dans l'eau
WO2011005917A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de blanchissage de tissus à l'aide d'une composition liquide de détergent pour le linge
EP2451919A1 (fr) 2009-07-09 2012-05-16 The Procter & Gamble Company Procédé de blanchissage des tissus à l'aide d'une composition liquide de détergent pour le linge
US20110005001A1 (en) 2009-07-09 2011-01-13 Eric San Jose Robles Detergent Composition
US20110005002A1 (en) 2009-07-09 2011-01-13 Hiroshi Oh Method of Laundering Fabric
EP2451925A1 (fr) * 2009-07-09 2012-05-16 The Procter & Gamble Company Procédé de lessive d'un tissu utilisant une composition détergente de lessive compactée
WO2011005623A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Composition détergente pour lessive comprenant de faibles taux d'agent de blanchiment
EP2451915A1 (fr) 2009-07-09 2012-05-16 The Procter & Gamble Company Composition catalytique de détergent pour le linge comprenant des taux relativement faibles d'électrolyte soluble dans l'eau
WO2011005813A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé pour laver des textiles à l'aide d'une composition détergente de lavage sous forme de tablettes
WO2011005911A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de blanchissage de tissus à l'aide d'une composition de détergent liquide concentrée
WO2011005630A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de lessive d'un tissu utilisant une composition détergente de lessive compactée
WO2011016958A2 (fr) 2009-07-27 2011-02-10 The Procter & Gamble Company Composition détergente
HUE029942T2 (en) 2009-08-13 2017-04-28 Procter & Gamble Method for washing low temperature fabrics
EP2302025B1 (fr) 2009-09-08 2016-04-13 The Procter & Gamble Company Composition de détergent pour linge comprenant des particules de cellulose de carboxyméthyle fortement solubles dans l'eau
EP2480652A1 (fr) 2009-09-23 2012-08-01 The Procter & Gamble Company Procédé pour préparer des particules séchées par pulvérisation
US20110300499A1 (en) 2009-10-07 2011-12-08 Leung Kwok Wai Simon Multiple temperature point control heater system
US20110152161A1 (en) 2009-12-18 2011-06-23 Rohan Govind Murkunde Granular detergent compositions comprising amphiphilic graft copolymers
US8334250B2 (en) 2009-12-18 2012-12-18 The Procter & Gamble Company Method of making granular detergent compositions comprising amphiphilic graft copolymers
EP2336283B1 (fr) 2009-12-18 2013-01-16 The Procter & Gamble Company Composition de nettoyage contenant de l'hémicellulose
DE102010001350A1 (de) 2010-01-29 2011-08-04 Evonik Goldschmidt GmbH, 45127 Neuartige lineare Polydimethylsiloxan-Polyether-Copolymere mit Amino- und/oder quaternären Ammoniumgruppen und deren Verwendung
BR112012018894A2 (pt) * 2010-01-29 2016-04-12 Procter & Gamble copolímeros de polidimetilsiloxano-poliéter lineares como grupos amino e/ou amônio quaternário e uso dos mesmos
US20110201533A1 (en) 2010-02-12 2011-08-18 Jennifer Beth Ponder Benefit compositions comprising polyglycerol esters
WO2011100420A1 (fr) 2010-02-12 2011-08-18 The Procter & Gamble Company Compositions avantageuses comportant des esters de polyglycérol réticulés
US20110201534A1 (en) 2010-02-12 2011-08-18 Jennifer Beth Ponder Benefit compositions comprising polyglycerol esters
WO2011100405A1 (fr) 2010-02-12 2011-08-18 The Procter & Gamble Company Compositions traitantes comprenant des esters de polyglycérol réticulés
US8859259B2 (en) 2010-02-14 2014-10-14 Ls9, Inc. Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
WO2011109322A1 (fr) 2010-03-04 2011-09-09 The Procter & Gamble Company Composition détergente
JP5563147B2 (ja) 2010-04-01 2014-07-30 ザ プロクター アンド ギャンブル カンパニー オルガノシリコーン
US20110257069A1 (en) 2010-04-19 2011-10-20 Stephen Joseph Hodson Detergent composition
EP2380960A1 (fr) 2010-04-19 2011-10-26 The Procter & Gamble Company Composition de détergent
US8889612B2 (en) 2010-04-19 2014-11-18 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
US20110257060A1 (en) 2010-04-19 2011-10-20 Robert Richard Dykstra Laundry detergent composition comprising bleach particles that are suspended within a continuous liquid phase
US20110257062A1 (en) 2010-04-19 2011-10-20 Robert Richard Dykstra Liquid laundry detergent composition comprising a source of peracid and having a ph profile that is controlled with respect to the pka of the source of peracid
EP2569408A1 (fr) 2010-05-12 2013-03-20 The Procter and Gamble Company Polymères de soins
WO2011141497A1 (fr) 2010-05-12 2011-11-17 Basf Se Compositions comprenant des polymères d'entretien
BR112012029188B1 (pt) 2010-05-18 2020-12-08 Milliken & Company compostos clareadores óticos e composições compreendendo os mesmos
WO2011146604A2 (fr) 2010-05-18 2011-11-24 Milliken & Company Azurants optiques et compositions les comportant
US8476216B2 (en) 2010-05-28 2013-07-02 Milliken & Company Colored speckles having delayed release properties
US8470760B2 (en) 2010-05-28 2013-06-25 Milliken 7 Company Colored speckles for use in granular detergents
EP2395070A1 (fr) 2010-06-10 2011-12-14 The Procter & Gamble Company Composition détergente liquide pour linge comprenant une lipase d'origine bactérienne
JP5710756B2 (ja) 2010-06-23 2015-04-30 ザ プロクター アンド ギャンブルカンパニー 汚れた布地の前処理及び洗濯方法並びに洗濯用製品
CN102971453B (zh) 2010-07-02 2015-08-12 宝洁公司 包含非香料活性剂的长丝、非织造纤维网和制备它们的方法
RU2553295C2 (ru) 2010-07-02 2015-06-10 Дзе Проктер Энд Гэмбл Компани Моющий продукт и способы его изготовления
CA2803629C (fr) 2010-07-02 2015-04-28 The Procter & Gamble Company Filaments comprenant des bandes non tissees avec agent actif et procedes de fabrication associes
RU2640933C1 (ru) 2010-07-02 2018-01-12 Дзе Проктер Энд Гэмбл Компани Филаменты, содержащие пригодные для перорального введения активные компоненты, нетканые полотна и способы их изготовления
JP5759544B2 (ja) 2010-07-02 2015-08-05 ザ プロクター アンド ギャンブルカンパニー 活性剤を送達する方法
RU2543892C2 (ru) 2010-07-02 2015-03-10 Дзе Проктер Энд Гэмбл Компани Способ получения пленок из нетканых полотен
WO2012009660A2 (fr) 2010-07-15 2012-01-19 The Procter & Gamble Company Compositions détergentes contenant des alcools gras et des dérivés de ceux-ci produits par voie microbienne
CN103097464A (zh) 2010-09-20 2013-05-08 宝洁公司 非含氟聚合物表面保护组合物
EP2619299B1 (fr) 2010-09-20 2018-02-28 Wacker Chemie AG Formulations soins du linge et procédés
EP2619271B1 (fr) 2010-09-20 2018-05-16 The Procter and Gamble Company Composition de protection des surfaces exempte de polymère fluoré
WO2012054058A1 (fr) 2010-10-22 2012-04-26 The Procter & Gamble Company Colorants bis-azoïques destinés à être utilisés à titre d'agents de bleuissement
BR112013009698B1 (pt) 2010-10-22 2020-04-28 Milliken & Co composto de agentes de azulagem
US20120101018A1 (en) 2010-10-22 2012-04-26 Gregory Scot Miracle Bis-azo colorants for use as bluing agents
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
EP2638113B1 (fr) 2010-11-12 2017-01-04 Milliken & Company Teintures thiophène azo et compositions de blanchisserie les contenant
WO2011011799A2 (fr) 2010-11-12 2011-01-27 The Procter & Gamble Company Colorants azoïques thiophéniques et compositions de lessive les contenant
WO2012116023A1 (fr) 2011-02-25 2012-08-30 Milliken & Company Capsules et compositions les comprenant
BR112013022921A2 (pt) 2011-03-07 2016-12-06 Procter & Gamble Comapny composições detergentes multiuso
US9163146B2 (en) 2011-06-03 2015-10-20 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US20120324655A1 (en) 2011-06-23 2012-12-27 Nalini Chawla Product for pre-treatment and laundering of stained fabric
EP2725912A4 (fr) 2011-06-29 2015-03-04 Solae Llc Compositions alimentaires destinées à être cuites au four et contenant des protéines de lait de soja isolées à partir de flux de traitement
EP2737043B1 (fr) 2011-07-25 2017-01-04 The Procter and Gamble Company Détergents présentant une couleur acceptable
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
MX342855B (es) 2011-08-15 2016-10-13 Procter & Gamble Composiciones detergentes que contienen compuestos de piridinol-n-oxido.
US20130072416A1 (en) 2011-09-20 2013-03-21 The Procter & Gamble Company High suds detergent compositions comprising isoprenoid-based surfactants
CA2849269A1 (fr) 2011-09-20 2013-03-28 The Procter & Gamble Company Compositions detergentes comprenant des rapports de melange specifiques d'agents tensio-actifs a base d'isoprenoide
AR088442A1 (es) 2011-09-20 2014-06-11 Procter & Gamble Composiciones detergentes que comprenden sistemas surfactantes primarios que comprenden surfactantes con base en isoprenoides altamente ramificados y otros surfactantes
AR088758A1 (es) 2011-09-20 2014-07-02 Procter & Gamble Composiciones detergentes de facil enjuague que comprenden surfactantes basados en isoprenoides
AR090031A1 (es) 2011-09-20 2014-10-15 Procter & Gamble Composiciones detergentes que comprenden sistemas tensioactivos sostenibles que comprenden tensioactivos derivados de isoprenoide
EP2581438A1 (fr) 2011-10-12 2013-04-17 The Procter and Gamble Company Composition de détergent
EP2773321B1 (fr) 2011-11-04 2015-09-09 Akzo Nobel Chemicals International B.V. Copolymères dendritiques greffés, et procédés de production associés
WO2013064647A1 (fr) 2011-11-04 2013-05-10 Akzo Nobel Chemicals International B.V. Copolymères dendritiques hybrides, compositions les comprenant et procédés de production associés
CA2853248A1 (fr) 2011-11-11 2013-05-16 Basf Se Compositions de polyolefine auto-emulsionnables
US20130118531A1 (en) 2011-11-11 2013-05-16 The Procter & Gamble Company Emulsions containing polymeric cationic emulsifiers, substance and process
MX352942B (es) 2012-01-04 2017-12-14 Procter & Gamble Estructuras fibrosas que contienen activos y multiples regiones que tienen densidades diferentes.
CN106968050B (zh) 2012-01-04 2019-08-27 宝洁公司 具有多个区域的含活性物质纤维结构
RU2655288C1 (ru) 2012-01-04 2018-05-24 Дзе Проктер Энд Гэмбл Компани Волокнистые структуры, содержащие частицы, и способы их изготовления
AR092788A1 (es) 2012-01-18 2015-05-06 Procter & Gamble Composiciones detergentes acidas para lavanderia
US8853142B2 (en) 2012-02-27 2014-10-07 The Procter & Gamble Company Methods for producing liquid detergent products
CN104508103A (zh) 2012-07-26 2015-04-08 宝洁公司 含酶的低ph液体清洁组合物
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
EP2708588A1 (fr) 2012-09-14 2014-03-19 The Procter & Gamble Company Composition de traitement de tissu
EP2708589A1 (fr) 2012-09-14 2014-03-19 The Procter & Gamble Company Composition de traitement de tissu
EP2708592B2 (fr) 2012-09-14 2022-03-16 The Procter & Gamble Company Composition de traitement de tissu
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye
EP2969020B1 (fr) 2013-03-15 2017-11-29 The Procter and Gamble Company Matériaux fonctionnels non saturés et ramifiés spécifiques pour leur utilisation dans des produits de consommation
CN105073966B (zh) 2013-03-28 2018-03-23 宝洁公司 包含聚醚胺的清洁组合物
EP2832841B1 (fr) 2013-07-30 2016-08-31 The Procter & Gamble Company Procédé de fabrication de compositions détergentes comprenant des polymères
EP2832843B1 (fr) 2013-07-30 2019-08-21 The Procter & Gamble Company Procédé de fabrication de compositions détergentes granulaires comprenant des polymères
PL2832842T3 (pl) 2013-07-30 2019-09-30 The Procter & Gamble Company Sposób wytwarzania kompozycji granulowanych detergentów zawierających środki powierzchniowo czynne
EP2832844A1 (fr) 2013-07-30 2015-02-04 The Procter & Gamble Company Procédé de fabrication de compositions détergentes comprenant des polymères
EP2862921A1 (fr) 2013-10-17 2015-04-22 The Procter and Gamble Company Composition liquide pour lessive comprenant un polymère alcoxylé et un colorant de nuançage
EP2870957A1 (fr) * 2013-11-07 2015-05-13 OTC GmbH Concentré aqueux à base d'iséthionate optiquement transparent à usage cosmétique
US20150150768A1 (en) 2013-12-04 2015-06-04 Los Alamos National Security Llc Furan Based Composition
MX2016007157A (es) 2013-12-09 2016-07-21 Procter & Gamble Estructuras fibrosas que incluyen un agente activo y tienen un grafico impreso sobre estas.
EP3092293A1 (fr) * 2014-01-08 2016-11-16 The Procter & Gamble Company Détergents pour lessive liquides à profil d'eau savonneuse amélioré
EP2899259A1 (fr) 2014-01-22 2015-07-29 The Procter and Gamble Company Compositions détergentes
US9719052B2 (en) 2014-03-27 2017-08-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
US20150275143A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
WO2015187757A1 (fr) 2014-06-06 2015-12-10 The Procter & Gamble Company Composition détergente comprenant des polymères à base de polyalkylèneimine
WO2016003699A1 (fr) 2014-06-30 2016-01-07 The Procter & Gamble Company Composition de lessive
HUE038165T2 (hu) 2014-08-07 2018-10-29 Procter & Gamble Mosószerkészítmény
HUE042647T2 (hu) 2014-08-07 2019-07-29 Procter & Gamble Mosószerkészítmény
WO2016023145A1 (fr) 2014-08-11 2016-02-18 The Procter & Gamble Company Détergent textile
CA2956081C (fr) 2014-08-27 2021-03-16 The Procter & Gamble Company Composition detergente comprenant un polymere cationique
JP6479959B2 (ja) 2014-08-27 2019-03-06 ザ プロクター アンド ギャンブル カンパニー カチオン性ポリマーを含む洗剤組成物
JP6400837B2 (ja) 2014-08-27 2018-10-03 ザ プロクター アンド ギャンブル カンパニー 布地の処理方法
US9809782B2 (en) 2014-08-27 2017-11-07 The Procter & Gamble Company Detergent composition comprising a cationic polymer and anionic/nonionic surfactant mixture
EP3197992B1 (fr) 2014-09-25 2023-06-28 The Procter & Gamble Company Compositions d'entretien de tissus contenant une polyétheramine
US10182980B2 (en) 2015-01-28 2019-01-22 The Procter & Gamble Company Method of making an amino silicone nanoemulsion
US9982223B2 (en) 2015-01-28 2018-05-29 The Procter & Gamble Company Amino silicone nanoemulsion
US9506019B2 (en) 2015-01-28 2016-11-29 The Procter & Gamble Company Silicone nanoemulsion comprising alkylene glycol alkyl ether
US20160230124A1 (en) 2015-02-10 2016-08-11 The Procter & Gamble Company Liquid laundry cleaning composition
US10155868B2 (en) 2015-10-13 2018-12-18 Milliken & Company Whitening agents for cellulosic substrates
US10597614B2 (en) 2015-10-13 2020-03-24 The Procter & Gamble Company Whitening agents for cellulosic substrates
US9902923B2 (en) 2015-10-13 2018-02-27 The Procter & Gamble Company Polyglycerol dye whitening agents for cellulosic substrates
US9976035B2 (en) 2015-10-13 2018-05-22 Milliken & Company Whitening agents for cellulosic substrates
US9777250B2 (en) 2015-10-13 2017-10-03 Milliken & Company Whitening agents for cellulosic substrates
US9745544B2 (en) 2015-10-13 2017-08-29 The Procter & Gamble Company Whitening agents for cellulosic substrates
US10308900B2 (en) 2015-12-22 2019-06-04 Milliken & Company Occult particles for use in granular laundry care compositions
EP3405604A1 (fr) 2016-01-21 2018-11-28 The Procter and Gamble Company Éléments fibreux comprenant du polyoxyde d'éthylène
US9719056B1 (en) 2016-01-29 2017-08-01 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US11682319B2 (en) 2016-03-10 2023-06-20 Intuitive Surgical Operations, Inc. Fake blood for use in simulated surgical procedures
CA3022686C (fr) 2016-05-23 2021-03-23 The Procter & Gamble Company Procede d'individualisation de trichomes
US20180072970A1 (en) 2016-09-13 2018-03-15 The Procter & Gamble Company Stable violet-blue to blue imidazolium compounds
US11697905B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles that exhibit consumer acceptable article in-use properties
WO2018140472A1 (fr) 2017-01-27 2018-08-02 The Procter & Gamble Company Articles contenant des agents actifs présentant des propriétés d'utilisation d'articles acceptables pour le consommateur
US11697906B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles and product-shipping assemblies for containing the same
US11697904B2 (en) 2017-01-27 2023-07-11 The Procter & Gamble Company Active agent-containing articles that exhibit consumer acceptable article in-use properties
US20200078759A1 (en) 2018-09-07 2020-03-12 The Procter & Gamble Company Methods and Systems for Forming Microcapsules
US20200078757A1 (en) 2018-09-07 2020-03-12 The Procter & Gamble Company Methods and Systems for Forming Microcapsules
US20200078758A1 (en) 2018-09-07 2020-03-12 The Procter & Gamble Company Methods and Systems for Forming Microcapsules
US11850293B2 (en) 2018-09-21 2023-12-26 The Procter & Gamble Company Active agent-containing matrix particles and processes for making same
US11518963B2 (en) 2018-10-18 2022-12-06 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11466122B2 (en) 2018-10-18 2022-10-11 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11299591B2 (en) 2018-10-18 2022-04-12 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US20200123475A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US11732218B2 (en) 2018-10-18 2023-08-22 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US20200123472A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US20200123319A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
CN113166680A (zh) 2018-12-14 2021-07-23 宝洁公司 包含颗粒的发泡纤维结构及其制备方法
CN113166679A (zh) 2018-12-14 2021-07-23 宝洁公司 遇水崩解型泡沫产生制品
US11485934B2 (en) 2019-08-02 2022-11-01 The Procter & Gamble Company Foaming compositions for producing a stable foam and methods for making same
US20210148044A1 (en) 2019-11-15 2021-05-20 The Procter & Gamble Company Graphic-Containing Soluble Articles and Methods for Making Same
WO2021156297A1 (fr) 2020-02-03 2021-08-12 Arch Uk Biocides Ltd Compositions de désinfection du linge et procédé d'utilisation
BR112022016120A2 (pt) 2020-02-14 2022-10-18 Procter & Gamble Polímero de enxerto, processo para obter um polímero de enxerto, e, produto para o cuidado de tecidos e da casa
WO2021165468A1 (fr) 2020-02-21 2021-08-26 Basf Se Polyalkylène-imines alcoxylées ou polyamines alcoxylées à biodégradabilité améliorée
US11718814B2 (en) 2020-03-02 2023-08-08 Milliken & Company Composition comprising hueing agent
US20210269747A1 (en) 2020-03-02 2021-09-02 Milliken & Company Composition Comprising Hueing Agent
US12031113B2 (en) 2020-03-02 2024-07-09 Milliken & Company Composition comprising hueing agent
CN116018394A (zh) 2020-08-26 2023-04-25 联合利华知识产权控股有限公司 包含羟乙基磺酸盐表面活性剂的洗涤剂组合物
WO2022104631A1 (fr) 2020-11-19 2022-05-27 The Procter & Gamble Company Procédé de fabrication de compositions de détergent comprenant un parfum
EP4011933A1 (fr) 2020-12-11 2022-06-15 Basf Se Polymère biodégradable amélioré avec avantage de performance de lavage primaire
JP2024508345A (ja) 2020-12-15 2024-02-27 ベーアーエスエフ・エスエー 生分解性ポリマー
EP4267656A1 (fr) 2020-12-23 2023-11-01 Basf Se Polyalkylène imines alcoxylées ou polyamines alcoxylées amphiphiles
CN116348524A (zh) 2020-12-23 2023-06-27 巴斯夫欧洲公司 新型烷氧基化聚烯亚胺或烷氧基化聚胺
WO2022197295A1 (fr) 2021-03-17 2022-09-22 Milliken & Company Colorants polymères à tachage réduit
US20240247209A1 (en) 2021-05-18 2024-07-25 Nouryon Chemicals International B.V. Polyester polyquats in cleaning applications
US20240158557A1 (en) 2021-05-20 2024-05-16 Nouryon Chemicals International B.V. Manufactured polymers having altered oligosaccharide or polysaccharide functionality or narrowed oligosaccharide distribution, processes for preparing them, compositions containing them, and methods of using them
EP4347933A1 (fr) 2021-05-28 2024-04-10 The Procter & Gamble Company Éléments fibreux à base de polymère naturel comprenant un tensioactif et leurs procédés de fabrication
AU2022293959A1 (en) 2021-06-18 2024-01-04 Basf Se Biodegradable graft polymers
WO2023275269A1 (fr) 2021-06-30 2023-01-05 Nouryon Chemicals International B.V. Concentrés liquides tensioactifs amphotères de chélates et leur utilisation dans des applications de nettoyage
CA3228918A1 (fr) 2021-08-10 2023-02-16 Nippon Shokubai Co., Ltd. Compose a teneur en oxyde de polyalkylene
EP4384562A1 (fr) 2021-08-12 2024-06-19 Basf Se Polymères greffés biodégradables
EP4134420A1 (fr) 2021-08-12 2023-02-15 The Procter & Gamble Company Composition détergente comprenant un tensioactif détergent et des polymères greffés biodégradables
EP4134421A1 (fr) 2021-08-12 2023-02-15 The Procter & Gamble Company Composition détergente comprenant un tensioactif détergent et un polymère greffé
JP2024531178A (ja) 2021-08-12 2024-08-29 ビーエーエスエフ ソシエタス・ヨーロピア 移染を防止するための生分解性グラフトポリマー
MX2024001864A (es) 2021-08-12 2024-03-01 Basf Se Polimeros de injerto biodegradables.
WO2023021101A1 (fr) 2021-08-19 2023-02-23 Basf Se Polyalkylène-imines alcoxylées modifiées
CN117881723A (zh) 2021-08-19 2024-04-12 巴斯夫欧洲公司 可通过包括步骤a)至d)的方法获得的改性的烷氧基化聚亚烷基亚胺和改性的烷氧基化多胺
EP4388031A1 (fr) 2021-08-19 2024-06-26 Basf Se Oligoalkylèneimines alcoxylées modifiées et oligoamines alcoxylées modifiées
JP2024531324A (ja) 2021-08-19 2024-08-29 ビーエーエスエフ ソシエタス・ヨーロピア 修飾アルコキシル化ポリアルキレンイミン又は修飾アルコキシル化ポリアミン
CN118139794A (zh) 2021-10-25 2024-06-04 联合利华知识产权控股有限公司 膜和胶囊
MX2024007601A (es) 2021-12-20 2024-07-09 Basf Se Polimeros de polipropilenimina (ppi), su preparacion, usos, y composiciones que comprenden dichos ppi.
WO2023117895A1 (fr) 2021-12-21 2023-06-29 Basf Se Passeport de produit chimique pour données de production
WO2024017797A1 (fr) 2022-07-21 2024-01-25 Basf Se Polymères greffés biodégradables utiles pour inhiber le transfert des couleurs
WO2024042005A1 (fr) 2022-08-22 2024-02-29 Basf Se Procédé de production d'esteramines sulfatées
WO2024119440A1 (fr) 2022-12-08 2024-06-13 Basf Se Copolymères multiblocs biodégradables comprenant des unités de liaison dérivées d'acétal de cétène cyclique
WO2024126268A1 (fr) 2022-12-12 2024-06-20 Basf Se Polymères greffés biodégradables pour inhibition de transfert de colorant
WO2024126267A1 (fr) 2022-12-12 2024-06-20 Basf Se Polymères greffés biodégradables
WO2024126270A1 (fr) 2022-12-12 2024-06-20 Basf Se Polymères greffés biodégradables en tant qu'inhibiteurs de transfert de colorant
DE102023135175A1 (de) 2022-12-16 2024-06-27 Basf Se Verfahren zur Herstellung von Aminosäureestern und organischen Sulfonsäuresalzen sowie Aminosäureestern und deren Salzen
WO2024175409A1 (fr) 2023-02-21 2024-08-29 Basf Se Polyalkylène imines alcoxylées hyper-ramifiées modifiées
WO2024175401A1 (fr) 2023-02-21 2024-08-29 Basf Se Polyalkylène imines alcoxylées modifiées ou polyamines alcoxylées modifiées
WO2024175407A1 (fr) 2023-02-21 2024-08-29 Basf Se Polyalkylène imines alcoxylées modifiées ou polyamines alcoxylées modifiées
WO2024180261A2 (fr) 2023-03-02 2024-09-06 Basf Se Oxyde d'éthylène respectueux de l'environnement, oxyde de propylène et produits en aval
WO2024188713A1 (fr) 2023-03-13 2024-09-19 Basf Se Polymères contenant de l'azote alcoxylé et leur utilisation
WO2024200177A1 (fr) 2023-03-24 2024-10-03 Basf Se Procédé de préparation d'esters d'acides aminés en tant que sels de sulfate d'organoéther à partir d'alcools alcoxylés

Family Cites Families (82)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE13746C (de) * H. BUDEL-MANN und J. F. AHLERS in Bremen Neuerungen an Hobelmaschinen
DE23346C (de) * C. JEDDING in Oythe, Oldenburg Neuerungen an Strohschüttlern für Dreschmaschinen
DD53839A (fr) *
US2016962A (en) * 1932-09-27 1935-10-08 Du Pont Process for producing glucamines and related products
US1985424A (en) * 1933-03-23 1934-12-25 Ici Ltd Alkylene-oxide derivatives of polyhydroxyalkyl-alkylamides
GB420518A (en) * 1933-03-23 1934-11-23 Ici Ltd Textile assistants
GB519381A (en) * 1937-09-21 1940-03-26 Du Pont Manufacture of maltosamines
US2653932A (en) * 1949-10-20 1953-09-29 Commercial Solvents Corp Amide-glycamine condensation products
US2703798A (en) * 1950-05-25 1955-03-08 Commercial Solvents Corp Detergents from nu-monoalkyl-glucamines
US2662073A (en) * 1951-04-27 1953-12-08 Charles L Mehltretter Gluconamides
US2717894A (en) * 1951-05-19 1955-09-13 Commercial Solvents Corp Sulfuric esters of acylated glucamines
GB745036A (en) * 1953-01-06 1956-02-15 Atlas Powder Co Improvements in or relating to heterocyclic amides and carboxylic esters thereof
GB771423A (en) * 1954-08-19 1957-04-03 Rohm & Haas Improvements in alkyl-n-sorbitylalkanamides
BE551361A (fr) * 1955-10-27
US2891052A (en) * 1956-04-10 1959-06-16 Rohm & Haas Anhydrosorbityl amides and process of preparation
BE557103A (fr) * 1956-05-14
US2982737A (en) * 1957-05-27 1961-05-02 Rohm & Haas Detergent bars
US2991296A (en) * 1959-02-26 1961-07-04 Oscar L Scherr Method for improving foam stability of foaming detergent composition and improved stabilizers therefor
US2994665A (en) * 1959-04-15 1961-08-01 Lever Brothers Ltd Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents
US3128287A (en) * 1963-01-31 1964-04-07 Pfizer & Co C 2,2'-oxodisuccinic acid, derivatives thereof, and process for preparing
US3308067A (en) * 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
FR1360018A (fr) * 1963-04-26 1964-04-30 Commercial Solvents Corp Solutions de formaldéhyde stabilisées, et leur procédé de stabilisation
DE1261861B (de) * 1963-08-22 1968-02-29 Dehydag Gmbh Verfahren zur Herstellung von Glycaminabkoemmlingen
US3285856A (en) * 1964-03-18 1966-11-15 Chevron Res Low foaming compositions having good detersive properties
US3312626A (en) * 1965-09-03 1967-04-04 Procter & Gamble Toilet bar
US3312627A (en) * 1965-09-03 1967-04-04 Procter & Gamble Toilet bar
NL136759C (fr) * 1966-02-16
SE319156B (fr) * 1966-08-01 1970-01-12 Henkel & Cie Gmbh
DK130418A (fr) * 1967-07-19
DE1619087A1 (de) * 1967-08-14 1969-10-02 Henkel & Cie Gmbh Als Textilwaschmittel brauchbare Tensidkombinationen sowie diese enthaltende Wasch- oder Waschhilfsmittel
US3635830A (en) * 1968-05-24 1972-01-18 Lever Brothers Ltd Detergent compositions containing oxydisuccing acid salts as builders
US3576749A (en) * 1969-02-06 1971-04-27 Procter & Gamble Soap toilet bars having improved smear characteristics
DK131638A (fr) * 1969-06-07
DE2038103A1 (de) * 1970-07-31 1972-02-10 Henkel & Cie Gmbh Waessrige Reinigungsmittelkonzentrate mit einem Gehalt an stabilisierten Enzymen
US4020015A (en) * 1971-10-12 1977-04-26 Lever Brothers Company Detergent compositions
DE2226872A1 (de) * 1972-06-02 1973-12-20 Henkel & Cie Gmbh Waschmittel mit einem gehalt an vergrauungsverhuetenden zusaetzen
US3920586A (en) * 1972-10-16 1975-11-18 Procter & Gamble Detergent compositions
US4605509A (en) * 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
DE2404070A1 (de) * 1974-01-29 1975-08-14 Henkel & Cie Gmbh Hautpflege- und hautschutzmittel mit einem gehalt an haut-feuchthaltemitteln
US3985669A (en) * 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US3929678A (en) * 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US3988255A (en) * 1975-03-05 1976-10-26 The Procter & Gamble Company Toilet bars
DE2613791A1 (de) * 1975-04-02 1976-10-21 Procter & Gamble Waschmittel
US4000093A (en) * 1975-04-02 1976-12-28 The Procter & Gamble Company Alkyl sulfate detergent compositions
US4094808A (en) * 1975-11-18 1978-06-13 Ppg Industries, Inc. Solubility stable encapsulated diperisophthalic acid compositions
US4129511A (en) * 1976-09-24 1978-12-12 The Lion Fat & Oil Co., Ltd. Method of spray drying detergents containing aluminosilicates
FR2390158A1 (fr) * 1977-05-10 1978-12-08 Oreal Compositions liquides de colorants de la famille des indoles destinees a la teinture des cheveux
US4116885A (en) * 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
EP0008830A1 (fr) * 1978-09-09 1980-03-19 THE PROCTER & GAMBLE COMPANY Compositions supprimant la mousse et détergents les contenant
DE2847438A1 (de) * 1978-11-02 1980-05-22 Henkel Kgaa Fluessiges, kaeltestabiles waschmittelkonzentrat
US4292212A (en) * 1978-11-29 1981-09-29 Henkel Corporation Shampoo creme rinse
FR2471777A1 (fr) * 1979-12-21 1981-06-26 Oreal Nouveaux agents cosmetiques a base de polymeres polycationiques, et leur utilisation dans des compositions cosmetiques
US4268406A (en) * 1980-02-19 1981-05-19 The Procter & Gamble Company Liquid detergent composition
DE3168008D1 (en) * 1980-04-24 1985-02-14 Procter & Gamble Liquid detergent compositions
US4540821A (en) * 1981-01-26 1985-09-10 Texaco Inc. Aminopolyols from sugars
US4483780A (en) * 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4565647B1 (en) * 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
EP0112344A1 (fr) * 1982-06-11 1984-07-04 National Research Development Corporation Composes amphipathiques
US4483781A (en) * 1983-09-02 1984-11-20 The Procter & Gamble Company Magnesium salts of peroxycarboxylic acids
US4556510A (en) * 1983-06-30 1985-12-03 Hercules Incorporated Transparent liquid shower soap
US4607036A (en) * 1983-12-15 1986-08-19 Lever Brothers Company Preservative compositions employing anti-microbial morpholine derivatives
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
US4790856A (en) * 1984-10-17 1988-12-13 Colgate-Palmolive Company Softening and anti-static nonionic detergent composition with sulfosuccinamate detergent
DE3585505D1 (de) * 1984-12-21 1992-04-09 Procter & Gamble Blockpolyester und aehnliche verbindungen, verwendbar als verschmutzungsentferner in waschmittelzusammensetzungen.
JPS61172811A (ja) * 1985-01-25 1986-08-04 Kao Corp シヤンプ−組成物
US4689167A (en) * 1985-07-11 1987-08-25 The Procter & Gamble Company Detergency builder system
DE3536530A1 (de) * 1985-10-12 1987-04-23 Basf Ag Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut
DE3538451A1 (de) * 1985-10-29 1987-05-07 Sueddeutsche Zucker Ag Fettsaeureamide von aminopolyolen als nichtionogene tenside
US4663071A (en) * 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
US4711730A (en) * 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
DE3625931A1 (de) * 1986-07-31 1988-02-04 Sueddeutsche Zucker Ag Isomaltamine sowie deren n-acylderivate, verfahren zu deren herstellung und ihre verwendung
US4704224A (en) * 1986-10-27 1987-11-03 The Procter & Gamble Company Soap bar composition containing guar gum
US4721580A (en) * 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
ES2077948T3 (es) * 1987-03-06 1995-12-01 Kao Corp Preparacion para el cuidado externo de la piel.
DE3711776A1 (de) * 1987-04-08 1988-10-27 Huels Chemische Werke Ag Verwendung von n-polyhydroxyalkylfettsaeureamiden als verdickungsmittel fuer fluessige waessrige tensidsysteme
US4877896A (en) * 1987-10-05 1989-10-31 The Procter & Gamble Company Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US5151209A (en) * 1987-11-19 1992-09-29 The Procter & Gamble Company Shampoo compositions
US4968451A (en) * 1988-08-26 1990-11-06 The Procter & Gamble Company Soil release agents having allyl-derived sulfonated end caps
JPH03112904A (ja) * 1989-09-27 1991-05-14 Nippon Oil & Fats Co Ltd 抗菌剤
JPH0623087B2 (ja) * 1989-10-09 1994-03-30 花王株式会社 洗浄剤組成物
FR2657611A1 (fr) * 1990-02-01 1991-08-02 Rennes Ecole Nale Sup Chimie Nouveaux tensioactifs non ioniques derives de sucres: n-acylglycosylamines derives de mono- et di-saccharides et leurs procedes de fabrication.
JPH0756037B2 (ja) * 1990-04-02 1995-06-14 花王株式会社 洗浄剤組成物

Also Published As

Publication number Publication date
ES2079680T3 (es) 1996-01-16
CA2092186A1 (fr) 1992-03-29
JPH06501734A (ja) 1994-02-24
SK25293A3 (en) 1994-01-12
CA2092186C (fr) 1997-12-09
AU8854991A (en) 1992-04-28
DE69114716D1 (de) 1995-12-21
CN1035827C (zh) 1997-09-10
DE69114716T2 (de) 1996-06-13
CN1061242A (zh) 1992-05-20
TR26007A (tr) 1993-11-01
HU9300892D0 (en) 1993-07-28
WO1992006152A1 (fr) 1992-04-16
IE913411A1 (en) 1992-04-08
US5332528A (en) 1994-07-26
MX9101368A (es) 1992-05-04
NZ240028A (en) 1995-07-26
HUT64784A (en) 1994-02-28
EP0551390A1 (fr) 1993-07-21
TW223113B (fr) 1994-05-01
BR9106912A (pt) 1993-07-20

Similar Documents

Publication Publication Date Title
EP0551390B1 (fr) Amides de l'acide gras de polyhydroxy dans des compositions detergentes contenant un agent antisalissures
EP0551396B1 (fr) Compositions detergentes contenant des tensioactifs d'amides de l'acide gras de polyhydroxy et de sulfonates d'ester d'alkyle
EP0550695B1 (fr) Tensioactifs d'amides de l'acide gras de polyhydroxy destines a ameliorer l'efficacite des enzymes
EP0550557B1 (fr) Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide d'acide gras polyhydroxyle
EP0550606B1 (fr) Systemes tensioactifs non ioniques contenant des amides d'acides gras de polyhydroxy et un ou plusieurs tensioactifs non ioniques supplementaires
EP0550644B1 (fr) Compositions detergentes contenant un amide de l'acide gras de polyhydroxy et un sulfate d'alkyle alcoxyle
EP0550634B1 (fr) Amides d'acide gras de polyhydroxy compris dans des compositions detersives liquides contenant un agent d'azurage
US5700771A (en) Polyhydroxy fatty acid amide surfactants in percarbonate bleach-containing compositions
EP0551375B2 (fr) Amides de l'acide gras de polyhydroxy dans des detergents comportant un adjuvant a la zeolite ou au silicate stratifie
EP0550692B1 (fr) Compositions detergentes contenant un tensioactif d'amide de l'acide gras de polyhydroxy et un agent dispersant polymere
EP0551413B1 (fr) Compositions detergentes contenant un amide de l'acide gras de polyhydroxy et un sulfonate d'alkyle benzene
EP0551393B1 (fr) Amides de l'acide gras de polyhydroxy dans des detergents contenant des adjuvants au polycarboxylate
IE913414A1 (en) Detergent compositions containing polyhydroxy fatty acid¹amide and alkyl benzene sulfonate
IE913420A1 (en) Nonionic surfactant systems containing polyhydroxy fatty¹acid amides and one or more additional nonionic surfactants

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930311

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19930930

RBV Designated contracting states (corrected)

Designated state(s): BE DE ES FR GB IT NL SE

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL SE

REF Corresponds to:

Ref document number: 69114716

Country of ref document: DE

Date of ref document: 19951221

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2079680

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000620

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000807

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20000901

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000905

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20000926

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000928

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20001010

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010926

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010930

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 20010930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020501

EUG Se: european patent has lapsed

Ref document number: 91918418.4

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020531

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020401

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050925